CN1976957B - Polyethylene for injection moldings - Google Patents
Polyethylene for injection moldings Download PDFInfo
- Publication number
- CN1976957B CN1976957B CN2005800213007A CN200580021300A CN1976957B CN 1976957 B CN1976957 B CN 1976957B CN 2005800213007 A CN2005800213007 A CN 2005800213007A CN 200580021300 A CN200580021300 A CN 200580021300A CN 1976957 B CN1976957 B CN 1976957B
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- carbon atom
- group
- preferred
- methyl
- polyethylene
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- -1 Polyethylene Polymers 0.000 title claims abstract description 500
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 82
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 79
- 238000001746 injection moulding Methods 0.000 title abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 238000009826 distribution Methods 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 182
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 34
- 229920002554 vinyl polymer Polymers 0.000 claims description 34
- 230000002902 bimodal effect Effects 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 3
- 230000002180 anti-stress Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 65
- 238000000034 method Methods 0.000 abstract description 54
- 238000002360 preparation method Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 12
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 229920001519 homopolymer Polymers 0.000 abstract 1
- 150000001721 carbon Chemical group 0.000 description 135
- 150000003254 radicals Chemical class 0.000 description 125
- 239000002585 base Substances 0.000 description 116
- 229910052735 hafnium Inorganic materials 0.000 description 105
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 105
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 68
- 229910052736 halogen Inorganic materials 0.000 description 66
- 150000002367 halogens Chemical class 0.000 description 60
- 150000001875 compounds Chemical class 0.000 description 58
- 125000003118 aryl group Chemical group 0.000 description 57
- 229910052757 nitrogen Inorganic materials 0.000 description 53
- 239000001257 hydrogen Substances 0.000 description 50
- 229910052739 hydrogen Inorganic materials 0.000 description 50
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 49
- 125000003963 dichloro group Chemical group Cl* 0.000 description 47
- 229910052723 transition metal Inorganic materials 0.000 description 44
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 43
- 239000000203 mixture Substances 0.000 description 43
- 150000003624 transition metals Chemical class 0.000 description 43
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 42
- 239000000460 chlorine Substances 0.000 description 42
- 229910052801 chlorine Inorganic materials 0.000 description 42
- 125000000623 heterocyclic group Chemical group 0.000 description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 39
- 125000002877 alkyl aryl group Chemical group 0.000 description 39
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 39
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 38
- 229910052731 fluorine Inorganic materials 0.000 description 38
- 239000011737 fluorine Substances 0.000 description 38
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 37
- 229910052794 bromium Inorganic materials 0.000 description 37
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 37
- 229910052698 phosphorus Inorganic materials 0.000 description 37
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 36
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 36
- 150000002431 hydrogen Chemical class 0.000 description 36
- 125000000217 alkyl group Chemical group 0.000 description 35
- 229910052782 aluminium Inorganic materials 0.000 description 35
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 35
- 125000001072 heteroaryl group Chemical group 0.000 description 34
- 239000003446 ligand Substances 0.000 description 33
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 32
- 150000004698 iron complex Chemical class 0.000 description 30
- 238000007254 oxidation reaction Methods 0.000 description 29
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 28
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 28
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 27
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 27
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 27
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 27
- 125000004429 atom Chemical group 0.000 description 26
- 230000003647 oxidation Effects 0.000 description 26
- 230000004913 activation Effects 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 125000001424 substituent group Chemical group 0.000 description 24
- 239000011651 chromium Substances 0.000 description 23
- 239000000126 substance Substances 0.000 description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 22
- 239000004411 aluminium Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 22
- 229910052804 chromium Inorganic materials 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 21
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 239000011574 phosphorus Substances 0.000 description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 19
- 150000001408 amides Chemical class 0.000 description 19
- 125000003710 aryl alkyl group Chemical group 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 17
- 125000001624 naphthyl group Chemical group 0.000 description 17
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 16
- 239000012190 activator Substances 0.000 description 16
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 16
- 229910001701 hydrotalcite Inorganic materials 0.000 description 16
- 229960001545 hydrotalcite Drugs 0.000 description 16
- GUVXZFRDPCKWEM-UHFFFAOYSA-N pentalene Chemical compound C1=CC2=CC=CC2=C1 GUVXZFRDPCKWEM-UHFFFAOYSA-N 0.000 description 16
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000001354 calcination Methods 0.000 description 15
- 125000000753 cycloalkyl group Chemical group 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 13
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 229960001866 silicon dioxide Drugs 0.000 description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 229910000085 borane Inorganic materials 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 230000000737 periodic effect Effects 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 11
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 9
- 239000002841 Lewis acid Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 9
- 241000534944 Thia Species 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 229910052796 boron Inorganic materials 0.000 description 9
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 9
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 9
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 9
- 239000004913 cyclooctene Substances 0.000 description 9
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 9
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 9
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 9
- 125000006038 hexenyl group Chemical group 0.000 description 9
- 229910000765 intermetallic Inorganic materials 0.000 description 9
- 150000007517 lewis acids Chemical class 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 9
- 230000000379 polymerizing effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 150000003222 pyridines Chemical class 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 6
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000001188 haloalkyl group Chemical group 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 5
- 239000007848 Bronsted acid Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 125000000068 chlorophenyl group Chemical group 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000002075 main ingredient Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
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- C08F4/00—Polymerisation catalysts
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
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Abstract
Polyethylene which comprises ethylene homopolymers and/or copolymers of ethylene with 1- alkenes and has a molar mass distribution width MW/Mn of from 3 to 30, a density of from 0.945 to 0.965 g/cm<SUP>3</SUP>, a weight average molar mass Mw of from 50000 g/mol to 200000 g/mol, a HLMI of from 10 to 300 g/10 min and has from 0.1 to 15 branches/1000 carbon atoms, wherein the 1 to 15 percents by weight of the polyethylene having the highest molar masses have a degree of branching of more than 1 branch of side chains larger than CH<SUB>3</SUB>/1000 carbon atoms, a process for its preparation, catalysts suitable for its preparation and also injection moldings in which this polyethylene is present.
Description
The present invention relates to novel polyethylene, it comprises the multipolymer of Alathon and/or ethene and 1-alkene and has the molecular weight distribution width Mw/Mn of 3-30,0.945-0.965g/cm
3Density, 50000g/mol is to the weight-average molecular weight Mw of 200000g/mol, the HLMI of 10-300g/10min and have 0.1-15 branch/1000 carbon atom, wherein the polyethylene of 1-15wt% with highest weight have more than 1 greater than CH
3The degree of branching of branch/1000 carbon atom of side chain, catalyst composition and its preparation method, and the injection-molded item that has this polyethylene to exist.
Different poly blends is known and is used to prepare the injection-molded item with high anti-stress cracking, as disclosed in DE-C 34 37 116.
Recently, polyethylene blend has been used for the screw thread closer that many types are produced in injection moulding.If keep their size and dimension in the process of cooling of screw thread closer after the injection moulding program, promptly do not shrink (low-shrinkage), then be ideal.The key property of plastics has been represented in the maintenance that low-shrinkage is taken into account shape, and they for example are used to produce the screw thread closer with accurate cooperation.In addition, if the polyethylene molding composition melt form has good flowability, then injection moulding process carries out than being easier to usually.The requirement of increasing is day by day arranged for the physical strength that comprises poly moulded parts.On the other hand, the good workability of realizing high productivity is needed.
WO 00/71615 discloses from having 0.950-0.98g/cm
3The injection moulded containers that obtains of the bimodal polyethylene of degree of crystallinity of density, 60-90%, this bimodal polyethylene by at least 2 kinds have polyethylene component that different molecular weight distributes forms with at least a component wherein be the multipolymer of ethene.Polyethylene is to obtain via reactor cascade or the melt extrusion by two kinds of components.
Known ethylene copolymer blend thing is at good mechanical properties, remains unsafty on the high workability of melt and good optical properties comprehensive.
Find that surprisingly this problem can realize by using the specific catalyst composition, rely on said composition can prepare the polyethylene with good mechanical properties, good workability and good optical properties.
Therefore we found a kind of polyethylene, and it comprises the multipolymer of Alathon and/or ethene and 1-alkene, and have the molecular weight distribution width Mw/Mn of 3-30,0.945-0.965g/cm
3Density, 50000g/mol is to the weight-average molecular weight Mw of 200000g/mol, the HLMI of 10-300 g/10min and have 0.1-15 branch/1000 carbon atom, wherein the polyethylene of 1-15wt% with highest weight have more than 1 greater than CH
3The degree of branching of branch/1000 carbon atom of side chain.
We have also found injection-molded item, lid and closer that polyethylene wherein of the present invention exists as main ingredient.In addition, we have found that polyethylene of the present invention is used to produce the purposes of injection-molded item.
We have also had been found that preparation catalyst of polyethylene system of the present invention, and catalyst system is used for the polyreaction of ethene and/or is used for ethene and the purposes of the copolymerization of 1-alkene and prepare poly method of the present invention by the polyreaction of ethene and/or the copolymerization of ethene and 1-alkene in the presence of catalyst system.
Polyethylene of the present invention has at 3-30, the molecular weight distribution width Mw/Mn in preferred 5-20 and the preferred especially 6-15 scope.Poly density of the present invention is at 0.945-0.965g/cm
3, preferred 0.947-0.96g/cm
3Preferred especially 0.948-0.955g/cm
3In the scope.Poly weight-average molecular weight Mw of the present invention is at 50000g/mol-200000g/mol, in preferred 70000g/mol-150000g/mol and the preferred especially 80000g/mol-120000g/mol scope.Poly HLMI of the present invention is at 10-300g/10min, in the scope of preferred 50-200g/10min and preferred especially 70-150g/10min.For the present invention, this expression phrase " HLMI " refer to known " high load melt index " and according to ISO 1133 under the temperature of the load of 21.6kg and 190 ℃, measure (190 ℃/21.6kg).
This density [g/cm
3] measure according to ISO 1183.Molecular weight distribution and the average Mn that derives from from it, Mw, with the mensuration of Mw/Mn be by using method and placed in-line following chromatographic column based on DIN 55672, on WATERS 150C, undertaken by the high-temperature gel permeation chromatography method, placed in-line chromatographic column: 3x SHODEX AT 806MS, 1x SHODEX UT 807 and 1x SHODEX AT-G, operational condition: solvent: 1,2,4-trichlorobenzene (with 2 of 0.025wt%, 6-two-tertiary butyl-4-methylphenol is stable), flow velocity: 1ml/min, 500 μ l volume injected, temperature: 135 ℃, use the PE standard specimen to proofread and correct.Use WIN-GPC to estimate.
Polyethylene of the present invention has 0.1-15 branch/1000 carbon atom, preferred 0.2-8 branch/1000 carbon atom and preferred especially 0.3-3 branch/1000 carbon atom.This branch's number/1000 carbon atom is to utilize
13C-NMR, by James.C.Randall, JMS-REV.Macromol.Chem.Phys., C29 (2﹠amp; 3), the described method of 201-317 (1989) is measured, and refers to CH
3The total content of group/1000 carbon atom.
In addition, polyethylene of the present invention has the polyethylene with highest weight of 1-15wt%, preferred 2-12wt% and especially preferred 3-8wt%, and have more than 1 greater than CH
3Branch/1000 carbon atom of side chain, preferably at 2-20 greater than CH
3Side chain branch/1000 carbon atom and particularly preferably in 5-15 greater than CH
3The branch/1000 carbon atom scope of side chain in the degree of branching.This can be by being described in W.Holtrup, Makromol.Chem.178, and the solvent-nonsolvent stage division (latter is called the Holtrup stage division) in 2335 (1977) combines with the IR measurement of different fractions and measures.Dimethylbenzene under 130 ℃ and ethylene glycol diethyl ether are as the fractionated solvent.Use the polyethylene of 5g and be divided into 8 fractions.Each fraction subsequently by
13C-NMR composes mensuration.The degree of branching in each polymer fractions can be by James.C.Randall, JMS-REV.Macromol.Chem.Phys., C29 (2﹠amp; 3), 201-317 (1989) is described
13The C-NMR method is measured.
Polyethylene of the present invention preferably has and is lower than 50%, especially the CDBI of 10-45%.The method of measuring CDBI for example is described among the WO 93/03093.The TREF method for example is described in Wild, Advances in Polymer Science, and 98, p.1-47,57p.153 is in 1992.CDBI is defined as having the weight percent of copolymer molecule of the co-monomer content of average total comonomer molar content ± 25%.Greater than CH
3The branch of side chain refer at the content of disregarding side chain under the situation of end group/1000 carbon atom.
Poly molecular weight distribution of the present invention can be unimodal, bimodal or multimodal.In present patent application, monomodal molecular weight distribution refers to that molecular weight distribution has single maximum value.Bimodal molecular weight distribution refers to that for present patent application, this molecular weight distribution has at least two flex points at a flank (flank) that begins from maximum value.Molecular weight distribution is preferably unimodal or bimodal, and is especially bimodal.
When by gel permeation chromatography (GPC) classification, the polyethylene of the present invention of 1-15wt% has highest weight, preferred 2-12wt% and preferred especially 3-8wt%, this fraction (TREF) is measured by analysis temperature rising elution fractionation method (" analytical temperature rising elutionfractionation technique ") then, preferably do not demonstrate to have and be higher than 80 ℃, preferably be higher than 85 ℃ and especially preferably be higher than the high density polyethylene(HDPE) peak of 90 ℃ vertex.The content of polymkeric substance in the fraction that is obtained is by ft-ir measurement at various temperatures.TREF result also can define the isolating polyethylene fraction of short chain ramose preparation property of quantity by having and proofread and correct.The TREF method for example is described in Wild, Advances in PolymerScience, and 98, p.1-47,57p.153 is in 1992.
When polyethylene of the present invention is checked by TREF, when testting, be higher than 80 ℃ by GPC, preferably be higher than 85 ℃ and each fraction of especially preferably being higher than 90 ℃ vertex and only demonstrate the polyethylene that molecular weight is lower than 1Mio g/mol, opposite with the polyethylene that obtains with conventional Z-type catalyst.
Polyethylene of the present invention preferably has the long chain branching degree λ of 0-2 long chain branches/10 000 carbon atom and preferred especially 0.1-1.5 long chain branches/10 000 carbon atoms.This long chain branching degree λ is by for example being described in ACS Series 521,1993, polymkeric substance chromatogram (Chromatographyof Polymers), Ed.Theodore Provder; Simon Pang and Alfred Rudin: the size exclusion chromatogram of long chain branching degree assessment (Size-ExclusionChromatographic Assessment of Long-Chain Branch Frequency inPolyethylenes) in the polyethylene, the light scattering method in the 254-269 page or leaf is measured.
Preferably, the polyethylene of the present invention of 5-50 weight % with lowest molecular weight, preferred 10-40wt% and preferred especially 15-30 weight % have the degree of branching that is lower than 10 branch/1000 carbon atoms.The degree of branching in having that a part of polyethylene of lowest molecular weight is 0.01-9 branch/1000 carbon atom and preferred especially 0.1-6 branch/1000 carbon atom preferably.This can pass through described Holtrup/
13The C-NMR method is measured.This branch's number/1000 carbon atom is to utilize
13C-NMR, by James.C.Randall, JMS-REV.Macromol.Chem.Phys., C29 (2﹠amp; 3), the described method of 201-317 (1989) is measured, and refers to CH
3The total content of group/1000 carbon atom.
Polyethylene of the present invention has at least 0.2 vinyl/1000 carbon atom, preferred 0.7-5 vinyl/1000 carbon atom and preferred especially 0.9-3 vinyl/1000 carbon atom.The content of individual vinyl/1000 carbon atom is by IR, and ASTM D 6248-98 measures.For the present invention, expressing phrase " vinyl " refers to-CH=CH
2Group; Vinylidene (vinylidene) and inner ethylenic group are not included in this expression phrase.Vinyl is usually by owing to the polymkeric substance termination reaction after ethene inserts, and the normally formation afterwards of the polymkeric substance termination reaction after comonomer inserts of vinylidene end group.
Polyethylene of the present invention preferably have 0.01-20 greater than CH
3Branch/1000 carbon atom (the preferred C of side chain
2-C
6Side chain/1000 carbon atom), preferred 1-15 greater than CH
3Branch/1000 carbon atom (the preferred C of side chain
2-C
6Side chain/1000 carbon atom) and especially preferred 2-8 greater than CH
3Branch/1000 carbon atom (the preferred C of side chain
2-C
6Side chain/1000 carbon atom).Greater than CH
3Branch's number/1000 carbon atom of side chain be to utilize
13C-NMR, by James.C.Randall, JMS-REV.Macromol.Chem.Phys., C29 (2﹠amp; 3), the described method of 201-317 (1989) is measured, and refers to greater than CH
3The total content of the side chain of group/1000 carbon atom (disregarding end group).Particularly preferably being is having 1-butylene, have 0.01-20 ethyl, butyl or hexyl side branch/1000 carbon atoms in 1-hexene or the polyethylene of 1-octene, preferred 1-15 ethyl, butyl or hexyl side branch/1000 carbon atoms and preferred especially 2-8 ethyl, butyl or hexyl side branch/1000 carbon atoms as alpha-olefin.This refers to disregarding content/1000 carbon atom of ethyl under the situation of end group, butyl or hexyl side chain.
In polyethylene of the present invention, have and be lower than 10 000g/mol, the polyethylene part that preferably is lower than the molecular weight of 20 000g/mol preferably has 0-1.5 greater than CH
3Branch/1000 carbon atom (the preferred C of side chain
2-C
6Side chain/1000 carbon atom) the degree of branching.Particularly preferably be, have and be lower than 10000g/mol, preferably be lower than the polyethylene part of 20000g/mol, its have 0.1-0.9 greater than CH
3Branch/1000 carbon atom (the preferred C of side chain
2-C
6Side chain/1000 carbon atom) the degree of branching.Preferably, in the polyethylene of the present invention that has 1-butylene, 1-hexene or 1-octene as the 1-alkene, have the polyethylene part that is lower than 10000g/mol, preferably is lower than the molecular weight of 20000g/mol and preferably have the degree of branching of 0-1.5 ethyl, butyl or hexyl side chain branch/1000 carbon atoms.Particularly preferably be, have and be lower than 10000g/mol, preferably be lower than the polyethylene part of the molecular weight of 20000g/mol, it has the degree of branching of 0.1-0.9 ethyl, butyl or hexyl side chain branch/1000 carbon atoms.This can pass through described Holtrup/ equally
13The C-NMR method is measured.
In addition preferably, in polyethylene of the present invention at least 70% greater than CH
3The branch of side chain be present in the polyethylene of 50 weight % with highest weight.This can pass through described Holtrup/ equally
13The C-NMR method is measured.
Polyethylene of the present invention preferably has and is lower than 3, especially the mixing quality of measuring according to ISO 13949 of 0-2.5.This numerical value is the polyethylene that takes out from reactor based on directly,, does not have the polyethylene powders that melts in advance in forcing machine that is.This polyethylene powders preferably obtains by the polyreaction in single reactor.
Except the ethene in the poly ethylene copolymer part of the present invention, as the 1-alkene of the comonomer that can in ethylene copolymer, exist (separately or with the thing form that is mixed with each other), might use whole 1-alkenes with 3 to 12 carbon atoms, propylene for example, 1-butylene, 1-amylene, the 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene.This ethylene copolymer preferably includes the 1-alkene with 4 to 8 carbon atoms that presents the copolymerization form as comonomer unit, for example 1-butylene, 1-amylene, 1-hexene, 4-methylpentene or 1-octene.Particularly preferred being to use is selected from 1-butylene, the 1-alkene in 1-hexene and the 1-octene.Polyethylene of the present invention preferably includes 0.01-5 weight %, the comonomer of preferred 0.1-3 weight %.
Polyethylene of the present invention can further comprise 0-6 weight %, known auxiliary agent own and/or the additive of preferred 0.1-1 weight %, processing stabilizers for example, the stablizer of the effect of opposing light and heat, common additive such as lubricant, antioxidant, anti and static inhibitor, and, if suitable, dyestuff.The person skilled in the art is familiar with the type and the amount of these additives.
In addition, have been found that poly processing characteristics of the present invention can further be improved by the introducing of a spot of fluoroelastomer or thermoplastic polyester.This type of fluoroelastomer is known as processing aid and for example with trade(brand)name
With
(also referring to, for example US-A-3125547) is purchased.They are preferably with 10-1000ppm, and the amount of preferred especially 20-200ppm is added, based on the total mass according to blend polymer of the present invention.
Additive and poly common mixing of the present invention can be undertaken by whole known methods.This can, for example,, carry out in Farrel kneader or the Kobe kneader by powdery components being incorporated into for example twin screw kneader (ZSK) of prilling granulator.The mixture of granulation also can directly be processed on membrane production equipment.
We have had been found that also polyethylene of the present invention is used to produce the purposes of injection-molded item, and the purposes of producing the injection-molded item (preferred screw thread closer, lid, pipe shoulder and engineering part) that has polyethylene of the present invention to exist as main ingredient.
The injection-molded item that has polyethylene of the present invention to exist as main ingredient, screw thread closer and lid, pipe shoulder and engineering part are poly those products of the present invention that contain 50-100wt%, preferred 60-90wt%, based on the total polymer material of making usefulness.Especially, in wherein the poly injection-molded item of the present invention, screw thread closer and the lid that contain 50-100wt% of a layer in the middle of multilayer is also included within.
The polyethylene of the present invention of 1mm thickness and injection-molded item preferably have and are lower than 94%, the mist degree of preferred 10-92% and preferred especially 50-91%,, on BYKGardener Haze Guard Plus Device, measure according to ASTM D 1003-00 at film 10 * 10cm of at least 5.According to ISO DIS2 16770 under the pressure of 3.5Mbar and 80 ℃, the stress cracking resistance of measured polyethylene and injection-molded item in the 2 weight % solution that obtain soluble in water by AkropalN (N=10) (full notch creep test (FNCT)) is 5h at least preferably, preferred 6-80h and especially preferred 7-20h.The polyethylene of the present invention of 1mm thickness and injection-molded item preferably have the shock resistance of 12J at least, record under-20 ℃ according to the falling weight impact test instrument of ISO 6603.
Polyethylene can be processed on common injection moulding machine.Surface smoothness on the moulded parts that is obtained is uniformly and can be by improving injection rate or improving die temperature and further improved.
Flowing property under processing conditions is measured with spiral flow test.Polyethylene is to be expelled in the volution mould under temperature, pressure and the screw speed of regulation, obtains to have the spiral tube of various wall thickness.The length of the spiral tube that is obtained can be considered to mobile tolerance.Spiral flow test is that mold closing pressure and the 3mm mouth mould with 100t measured on Demag ET100-310.
Poly size and dimension stability of the present invention is to test by the thread cap that has screw diameter 28.2mm 180-270 ℃ of following injection moulding processing.This lid is cooled and measures the screw diameter of 50 samples, calculating mean value and with initial screw diameter contrast.The further visual inspection shape and size of sample stability.
Polyethylene of the present invention shows high flowing property, and wherein spiral tube length is greater than 40cm, and it is the material temperature at 250 ℃, the injection pressure of 1000 crust, and screw speed 90mm/s, 30 ℃ die temperature and wall thickness 2mm measure down.
The injection-molded item that has polyethylene of the present invention to exist as main ingredient, preferred closer, lid and screw thread closer and lid, pipe shoulder and engineering part are poly those products of the present invention that contain 50-100wt%, preferred 60-90wt%, based on the total polymer material of making usefulness.This thread cap and closer are preferred for bottle, the bottle of preferred drink.
But the catalyst system of polyethylene the application of the invention of the present invention and especially its preferred embodiment obtain.
The present invention further provides a kind of catalyst composition that comprises at least two kinds of different polymerizing catalysts, A wherein) be based on periodic table of elements 4-6 family metal monocyclopentadienyl title complex (its cyclopentadienyl system is not replaced to body by there being electric charge) (A1) or at least a polymerizing catalyst and the B of luxuriant hafnium (A2)) be to carry at least two neighbours to have, the iron component of the tridentate ligand of neighbour-dibasic aryl be the basis at least a polymerizing catalyst (B).
The present invention further provides the polymerization process of alkene in the presence of catalyst composition of the present invention.
For the present invention, no electric charge is the no electric charge functional group of element of containing 15 or 16 families of the periodic table of elements to body.
Luxuriant hafnium (Hafnocene) catalyst component for example is a cyclopentadienyl complex compound.This cyclopentadienyl complex compound can be, for example, be described in for example EP 129368, EP 561479, bridging among EP 545 304 and the EP 576 970 or bridging bicyclic pentadiene title complex not, be described in the monocyclopentadienyl title complex among the EP 416 815 for example such as the amido cyclopentadienyl complex compound of bridging, be described in the multinuclear cyclopentadienyl complex compound among the EP 632 063, be described in the tetrahydrochysene pentalene of the π-ligand-replacement among the EP659 758 or be described in the tetrahydroindene of the π-ligand-replacement among the EP 661 300.
Preferably contain general formula Cp-YmM
AThe monocyclopentadienyl title complex (A1) of following constitutional features (I), wherein variable has following meanings:
Cp is a cyclopentadienyl system,
Y is bonded in Cp and contains the substituting group that at least a no electric charge is given body, should contain at least a atom of the periodic table of elements 15 or 16 families to body,
M
ABe titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, especially chromium and
M is 1,2, or 3.
Suitable monocyclopentadienyl title complex (Al) contains general formula Cp-YmM
A(I) structural unit, wherein variable as defined above.Therefore other ligand can be bonded in atoms metal M
AOn.The quantity of other ligand depends on, for example, and the oxidation state of atoms metal.These ligands are not other cyclopentadienyl system.Suitable ligand comprises single anion and two anion ligands of having described for for example X.In addition, Lewis base such as amine, ether, ketone, aldehyde, ester, sulfide or phosphine also can be bonded on the metal center M.This monocyclopentadienyl title complex can be monomeric, dimerization or oligomeric form.This monocyclopentadienyl title complex is monomeric form preferably.
M
ABe to be selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, the metal in molybdenum and the tungsten.Transition metal M in the catalytic activity title complex
AOxidation state normally those in this area are known to the skilled.Chromium, molybdenum and tungsten probably exist with the state of oxidation+3, zirconium and hafnium with oxidation state+4 exist with titanium with oxidation state+3 or+4 exist.Yet, also might use such title complex, its oxidation state does not correspond to the oxidation state of active catalyst.Therefore this type of title complex can suitably reduce or oxidation by enough suitable activators.M
ATitanium (being in oxidation state 3) preferably, vanadium, chromium, molybdenum or tungsten.Particularly preferably be and be in oxidation state 2,3 and 4, especially 3 chromium.
M can be 1,2 or 3, promptly can be bonded on the Cp for body group Y for 1,2 or 3, and these can be identical or different when having two or three group Y.Preferably, only one be bonded in Cp for body group Y to go up (m=1).
It is the no electric charge functional group of element of containing 15 or 16 families of the periodic table of elements that this no electric charge is given body Y, amine for example, imines; carboxylic acid amides, carboxylicesters, ketone (oxo); ether; thioketones, phosphine, phosphorous acid ester; phosphine oxide; alkylsulfonyl, sulphonamide or unsubstituted, replacement or undersaturated heterocycle of condensed part or heteroaromatic rings system.Should can be connected to transition metal M at intermolecular or intramolecular bond to body Y
AGo up or be not bonded in it.Should preferably be connected to metal center M to body Y at intramolecular bond
AOn.Particularly preferably be and contain general formula Cp-Y-M
AThe monocyclopentadienyl title complex of structural unit.
Cp is a cyclopentadienyl system, the latter can be substituted by any way and/or condense with one or more aromatics, aliphatics, heterocycle or heteroaromatic rings, wherein 1,2 or 3 substituting group, preferred 1 substituting group, formed and/or 1,2 or 3 substituting group by group Y, preferred 1 substituting group is by group Y and/or carry 1,2 or 3 substituting groups, preferred 1 substituent aromatics, aliphatics, heterocycle or heteroaromatic fused rings replace.This cyclopentadienyi skeleton itself is the C with 6 πDian Zis
5Member ring systems, wherein in these carbon atoms also can be by nitrogen or phosphorus, preferred phosphorus, substitute.Preferably use not by heteroatoms alternate C
5Member ring systems.This cyclopentadienyi skeleton can, for example, be selected from N with containing, P, the heteroaromatic rings of at least one atom among O and the S condense or condense with aromatic ring.Condense finger heterocycle and cyclopentadienyi skeleton here, and share two atoms (preferred carbon atom).This cyclopentadienyl system is bonded in M
AOn.
Suitable especially monocyclopentadienyl title complex (A1) is such title complex, wherein Y be by group-Zk-A-formed and with cyclopentadienyl system Cp and M
AForm together and contain general formula Cp-Z
k-A-M
AThe monocyclopentadienyl title complex of structural unit (II), wherein variable has following meanings:
Cp-Z
k-A is
Wherein variable has following meanings:
E
1A-E
5AEach is a carbon or a no more than E naturally
1ATo E
5ABe phosphorus,
R
1A-R
4ABe hydrogen separately independently of one another, C
1-C
22-alkyl, C
2-C
22-alkenyl, C
6-C
22-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl, NR in alkyl
5A 2, N (SiR
5A 3)
2, OR
5A, OSiR
5A 3, SiR
5A 3, BR
5A 2, this organic radical R wherein
1A-R
4AAlso can be replaced and two ortho position radicals R by halogen
1A-R
4AAlso can link to each other form five-, six-or seven yuan-ring, and/or two ortho position radicals R
1A-R
4AContinuous formation contains and is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle,
Radicals R
5ABe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and have alkylaryl and two paired radicals R of 6-20 carbon atom in aryl moiety in moieties
5AAlso can link to each other forms five-or six-unit ring,
Z is the divalent abutment between A and Cp, and it is selected from following groups:
-BR
6A-,-BNR
6AR
7A-,-AIR
6A-,-Sn-,-O-,-S-,-SO-,-SO
2-,-NR
6A-,-CO-,-PR
6A-or-P (O) R
6A-,
Wherein
L
1A-L
3ABe silicon or germanium separately independently of one another,
R
6A-R
11ABe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and have the alkylaryl or the SiR of 6-20 carbon atom in aryl moiety in moieties
12A 3, this organic radical R wherein
6A-R
11AAlso can be replaced and two paired or adjacent radicals R by halogen
6A-R
11AAlso can link to each other form five-or six-ring and
Radicals R
12ABe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl or in moieties, have 1-10 carbon atom and in aryl moiety, have the alkylaryl of 6-20 carbon atom, C
1-C
10-alkoxyl group or C
6-C
10-aryloxy and two radicals R
12AAlso can link to each other form five-or six-ring and
A is that the no electric charge of one or more atoms that contains 15 and/or 16 families of the periodic table of elements is given the body group, preferably unsubstituted, replace or condensed heteroaromatic rings system,
M
ABe to be selected from titanium (being in oxidation state 3), vanadium, chromium, the metal in molybdenum and the tungsten, especially chromium and
K is 0 or 1.
In preferred cyclopentadienyl system Cp, whole E
1A-E
5ABe carbon.
The polyreaction performance of metal complexes can be by changing substituent R
1A-R
4AAnd be affected.Substituent quantity and type can have influence on the accessibility of polymeric alkene near atoms metal M of wanting.In this way, might improve activity and the selectivity of catalyzer for various monomers (especially huge monomer).Because substituting group also can have influence on the speed of the termination reaction of the polymer chain of growing, the molecular weight of the polymkeric substance that forms also can change in this way.Substituent R
1A-R
4AChemical structure therefore in wide region, change so that reach the result who is desireed and obtain the catalyst system of imagination in advance.Possible carbon organic substituent R
1A-R
4ABe following groups for example: hydrogen, the C of linearity or branching
1-C
22-alkyl, methyl for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, (it can and then carry C to 5-to the first cycloalkyl of 7-
1-C
10-alkyl and/or C
6-C
10-aryl is as substituting group), cyclopropyl for example, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, C
2-C
22-alkenyl (it can be linear, and keys ring-type or branching and wherein two can be inner or terminal), vinyl for example, 1-allyl group, 2-allyl group, the 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, C
6-C
22-aryl (it can be replaced by other alkyl), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2, the 6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl, or arylalkyl (it can be replaced by other alkyl), benzyl for example, adjacent-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein two radicals R
1A-R
4AAlso can link to each other forms 5-, 6-or 7-unit ring and/or two ortho position radicals R
1A-R
4ACan link to each other to form to contain is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle and/or this organic radical R
1A-R
4AAlso can be by halogen such as fluorine, chlorine or bromine replaces.In addition, R
1A-R
4ACan be amino N R
5A 2Or N (SiR
5A 3)
2, alkoxyl group or aryloxy OR
5A, dimethylamino for example, N-pyrrolidyl, picolinyl, methoxyl group, oxyethyl group or isopropoxy.At organo-siloxane substituting group SiR
5A 3In radicals R
5ACan be for R with above
1A-R
4AThe carbon organic group that described group is identical, wherein two radicals R
5AAlso can link to each other forms 5-or 6-unit ring, trimethyl silyl for example, triethylsilyl, the butyl dimetylsilyl, tributyl silyl, tri-tert silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.These SiR
5A 3Group also can link to each other via oxygen or nitrogen and form cyclopentadienyi skeleton, for example trimethyl silyl oxygen base, triethylsilyl oxygen base, butyl dimetylsilyl oxygen base, tributyl silyl oxygen base or tri-tert silyl oxygen base.Preferred radicals R
1A-R
4ABe hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, neighbour-dialkyl group-or the phenyl that replaces of adjacent-two chloro-, trialkyl-or three the chloro-phenyl, naphthyl, xenyl and the anthryl that replace.Possible organosilicon substituting group is especially, to have the trialkylsilkl of 1-10 carbon atom in alkyl, especially trimethyl silyl.
Two ortho position radicals R
1A-R
4AWith the E that carries them
1A-E
5ACan form the heterocycle that contains at least one atom (special preferred nitrogen and/or sulphur) that is selected from nitrogen, phosphorus, oxygen and the sulphur together, preferred heteroaromatic rings, the wherein E that in this heterocycle or heteroaromatic rings, exists
1A-E
5ACarbon preferably.The heterocycle and the heteroaromatic rings that preferably have the ring size of 5 or 6 ring atoms.Also containing one to four nitrogen-atoms and/or sulphur or Sauerstoffatom except carbon atom is 1 as the first heterocyclic example of the 5-of ring atom, 2-dihydrofuran, furans, thiophene, pyrroles isoxazole, 3-isothiazole, pyrazoles ， oxazole, thiazole, imidazoles, 1,2, the 4-oxadiazole, 1,2, the 5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-triazole and 1,2,4-triazole.The example that can contain the 6-unit heteroaryl of one to four nitrogen-atoms and/or phosphorus atom is a pyridine, phospha benzene, pyridazine, pyrimidine, pyrazine, 1,3,5-triazines, 1,2,4-triazine or 1,2,3-triazine.5-person and 6-unit heterocycle also can be by C
1-C
10-alkyl, C
6-C
10-aryl, in moieties, have 1-10 carbon atom and in aryl moiety, have the alkylaryl of 6-10 carbon atom, trialkylsilkl or halogen such as fluorine, chlorine or bromine, dialkyl amide, the alkylaryl acid amides, diaryl acid amides, alkoxyl group or aryloxy replace or condense with one or more aromatics or heteroaromatic rings.The example of benzo-fused 5-unit heteroaryl is an indoles, indazole, cumarone, thionaphthene, benzothiazole, benzoxazole and benzoglyoxaline.The example of the first heteroaryl of benzo-fused 6-is a chroman, chromene, quinoline, isoquinoline 99.9, cinnolines, phthalazines, quinazoline, quinoxaline, 1,10-phenanthroline and quinolizine.The heterocyclic naming ﹠ numbering derives from Lettau, Chemie der Heterocyclen, and first version, VEB, Weinheim 1979.This heterocycle/heteroaromatic preferably condenses via two keys of the C-C of heterocycle/heteroaromatic rings and cyclopentadienyi skeleton.Has a heteroatomic heterocycle/heteroaromatic rings preferably 2,3-or b-condensed.
Cyclopentadienyl system Cp with annelated heterocycles is, for example, the thia pentalene, 2-methyl thia pentalene, 2-ethyl thia pentalene, 2-sec.-propyl thia pentalene, 2-normal-butyl thia pentalene, 2-tertiary butyl thia pentalene, 2-trimethyl silyl thia pentalene, 2-phenyl thia pentalene, 2-naphthyl thia pentalene, 3-methyl sulfo-pentalene, 4-phenyl-2,6-dimethyl-1-sulfo-pentalene, 4-phenyl-2,6-diethyl-1-sulfo-pentalene, 4-phenyl-2,6-di-isopropyl-1-sulfo-pentalene, 4-phenyl-2,6-di-n-butyl-1-sulfo-pentalene, 4-phenyl-2, the two trimethyl silyls of 6--1-sulfo-pentalene, the azepine pentalene, 2-methyl azepine pentalene, 2-ethyl azepine pentalene, 2-sec.-propyl azepine pentalene, 2-normal-butyl azepine pentalene, 2-trimethyl silyl azepine pentalene, 2-phenyl azepine pentalene, 2-naphthyl azepine pentalene, 1-phenyl-2,5-dimethyl-1-azepine pentalene, 1-phenyl-2,5-diethyl-1-azepine pentalene, 1-phenyl-2,5-di-n-butyl-1-azepine pentalene, 1-phenyl-2,5-two-tertiary butyl-1-azepine pentalene, 1-phenyl-2,5-two-trimethyl silyl-1-azepine pentalene, the 1-tertiary butyl-2,5-dimethyl-1-azepine pentalene, oxa-pentalene, the phospha pentalene, 1-phenyl-2,5-dimethyl-1-phospha pentalene, 1-phenyl-2,5-diethyl-1-phospha pentalene, 1-phenyl-2,5-di-n-butyl-1-phospha pentalene, 1-phenyl-2,5-two-tertiary butyl-1-phospha pentalene, 1-phenyl-2,5-two-trimethyl silyl-1-phospha pentalene, 1-methyl-2,5-dimethyl-1-phospha pentalene, the 1-tertiary butyl-2,5-dimethyl-1-phospha pentalene, 7-ring penta [1,2] thiophene [3,4] cyclopentadiene or 7-ring penta [1,2] pyrroles [3,4] cyclopentadiene.
In further preferred cyclopentadienyl system Cp, four radicals R
1A-R
4A, promptly two pairs ortho position group forms two heterocycles, especially heteroaromatic rings.This heterocyclic system is with aforesaid those are identical.
Cyclopentadienyl system Cp with two fused heterocycles for example is 7-cyclopenta two thiophene, the two phosphorus heterocycle amylenes (phosphole) of 7-cyclopenta two pyrroles or 7-cyclopenta.
The synthesis example of this type of cyclopentadienyl system with annelated heterocycles is as being described among the above-mentioned WO 98/22486.At " metalorganic catalysts for synthesis andpolymerisation ", Springer Verlag 1999, people such as Ewen have described other synthetic methods of these cyclopentadienyl system in 150 following pages.
Particularly preferred substituent R
1A-R
4ABe aforesaid carbon organic substituent and the carbon organic substituent that forms ring-type condensed ring system, promptly with E
1A-E
5A-cyclopentadienyi skeleton (preferred C
5-cyclopentadienyi skeleton) form indenyl, benzo indenyl, phenanthryl, fluorenyl or tetrahydro indenyl system for example unsubstituted or that replace, and, especially, their preferred embodiment.
This type of cyclopentadienyl system (does not have group-Z-A-, it is preferably placed at 1) example be the 3-methyl cyclopentadienyl, 3-ethyl cyclopentadienyl, 3-sec.-propyl cyclopentadienyl, 3-tertiary butyl cyclopentadienyl, dialkyl group alkyl cyclopentadienyl such as tetrahydro indenyl, 2,4-dimethyl cyclopentadienyl or 3-methyl-5-tertiary butyl cyclopentadienyl, the trialkyl cyclopentadienyl is as 2,3,5-trimethylammonium cyclopentadienyl or tetraalkyl cyclopentadienyl are as 2,3,4,5-tetramethyl-ring pentadienyl, and indenyl, 2-methyl indenyl, the 2-ethyl-indenyl, 2-sec.-propyl indenyl, 3-methyl indenyl, benzo indenyl and 2-methyl benzo indenyl.This condensed ring system can be carried additional C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, NR in moieties
5A 2, N (SiR
5A 3)
2, OR
5A, OSiR
5A 3Or SiR
5A3, for example 4-methyl indenyl, 4-ethyl-indenyl, 4-sec.-propyl indenyl, 5-methyl indenyl, 4-phenyl indenyl, 5-methyl-4-phenyl indenyl, 2-methyl-4-phenyl indenyl or 4-naphthyl indenyl.
In particularly preferred embodiments, substituent R
1A-R
4AIn (preferred a R
2A) be C
6-C
22-aryl or in moieties, have 1-10 carbon atom and in aryl moiety, have the alkylaryl of 6-20 carbon atom, preferred C
6-C
22-aryl such as phenyl, naphthyl, xenyl, anthryl or phenanthryl, wherein this aryl also can be contained N-, P-, the substituting group of O-or S-, C
1-C
22-alkyl, C
2-C
22-alkenyl, halogen or have the haloalkyl or the halogen aryl of 1-10 carbon atom, for example adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2,6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4, the 5-trimethylphenyl, adjacent-,-, right-dimethylamino phenyl, adjacent-,-, right-p-methoxy-phenyl, adjacent-,-, right-fluorophenyl, adjacent-,-, right-chloro-phenyl-, adjacent-,-, right-trifluoromethyl, 2,3-, 2,4-, 2,5-or 2,6-difluorophenyl, 2,3-, 2,4-, 2,5-or 2,6-dichlorophenyl or 2,3-, 2,4-, 2,5-or 2,6-two (trifluoromethyl) phenyl replaces.As the substituent N-that contains on aryl, P-, the substituting group of O-or S-, C
1-C
22-alkyl, C
2-C
22-alkenyl, halogen or haloalkyl or halogen aryl with 1-10 carbon atom are preferably placed at the contraposition that is bonded in the key on the cyclopentadienyl rings.This aryl substituent can be on the ortho position of substituting group-Z-A keyed jointing or two substituting groups be positioned at 1,3 of cyclopentadienyl rings each other.-Z-A and aryl substituent preferably are present in 1,3 each other on cyclopentadienyl rings.
The same with the situation of metallocenes, monocyclopentadienyl title complex (A1) can be a chirality.Therefore, the substituent R of cyclopentadienyi skeleton
1A-R
4AIn one can have one or more chiral centres or this cyclopentadienyl system Cp itself can be enantiotopic, have only like this and when it is bonded on the transition metal M, just induce chirality (about the form of the chirality in cyclopentadienyl compounds, referring to R.Halterman, Chem.Rev.92, (1992), 965-994).
At cyclopentadienyl system Cp with do not have electric charge to give the abutment between the body A be divalent organic bridge base (k=1), it preferably by carbon containing-and/or siliceous-and/or boracic-the bridging unit form.Activity of such catalysts can be exerted one's influence by the length that changes the connection base between cyclopentadienyl system and A.Z preferably is bonded on the cyclopentadienyi skeleton of annelated heterocycles and then or fused aromatic ring.Therefore, if this heterocycle or aromatic ring condense on the prosposition of cyclopentadienyi skeleton, then Z is preferably placed on 1 or 4 of cyclopentadienyi skeleton.
At the possible carbon organic substituent R that connects on the basic Z
6A-R
11ABe, for example, following groups: hydrogen, the C of linearity or branching
1-C
20-alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, 5-is to the first cycloalkyl of 7-, this cycloalkyl and then portability C
6-C
10-aryl is as substituting group, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, C
2-C
20-alkenyl, this alkenyl can be that keys linearity, ring-type or branching and wherein two can be inner or terminal, for example vinyl, 1-allyl group, 2-allyl group, 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, the C that can be replaced by other alkyl
6-C
20-aryl, phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2,6-dimethyl benzene-1-base, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-Three methyl Benzene-1-base, or the arylalkyl that can be replaced by other alkyl, benzyl for example, adjacent-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein two R
6ATo R
11AAlso can link to each other and form 5-or 6-unit ring, for example hexanaphthene, and this organic radical R
6A-R
11AAlso can be by halogen such as fluorine, chlorine or bromine replaces, pentafluorophenyl group or two-3 for example, 5-trifluoromethylbenzene-1-base and alkyl or aryl.
At organosilicon substituting group SiR
12A 3In radicals R
12ACan be for R with above
6A-R
11AMentioned identical group, wherein two radicals R
12AAlso can link to each other forms 5-or 6-unit ring, trimethyl silyl for example, triethylsilyl, the butyl dimetylsilyl, tributyl silyl, tri-tert silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.Preferred radicals R
6A-R
11ABe hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, neighbour-dialkyl group-or the phenyl that replaces of two chloro-, trialkyl-or three the chloro-phenyl, naphthyl, xenyl and the anthryl that replace.
Particularly preferred substituent R
6ATo R
11ABe hydrogen, the C of linearity or branching
1-C
20-alkyl, methyl for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, C
6-C
20-aryl (it can be replaced by other alkyl), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2,6-dimethyl benzene-1-base, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-Three methyl Benzene-1-base, or arylalkyl (it can be replaced by other alkyl), benzyl for example, adjacent-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein two radicals R
6ATo R
11AAlso can link to each other and form 5-or 6-unit ring, for example hexanaphthene, and organic radical R
6A-R
2BAlso can be by halogen such as fluorine, chlorine or bromine (especially fluorine) replaces, pentafluorophenyl group or two-3 for example, 5-trifluoromethylbenzene-1-base and replaced by alkyl or aryl.Particularly preferably be methyl, ethyl, 1-propyl group, 2-sec.-propyl, 1-butyl, the 2-tertiary butyl, phenyl and pentafluorophenyl group.
Z is group-CR preferably
6AR
7A-,-SiR
6AR
7A-, especially-Si (CH
3)
2-,-CR
6AR
7ACR
8AR
9A-,-SiR
6AR
7ACR
8AR
9A-replace or unsubstituted 1,2-phenylene and especially-CR
6AR
7A-.Aforesaid substituent R
6A-R
11APreferred embodiment similarly be preferred examples here.Preferably ,-CR
6AR
7A-be-CHR
6A-,-CH
2-or-C (CH
3)
2-group.-L
1AR
6AR
7ACR
8AR
9A-in group-SiR
6AR
7A-can be bonded on the cyclopentadienyl system or be bonded on the A.This group-SiR
6AR
7A-or its preferred embodiment preferably be bonded on the Cp.
K is 0 or 1; Especially, k be 1 or when A be unsubstituted, replacement or also can be 0 during the condensed heterocycle system.Preferably k is 1.
A is the atom that contains 15 or 16 families of the periodic table of elements, preferably is selected from oxygen, sulphur, and the no electric charge of the one or more atoms in nitrogen and the phosphorus (preferred nitrogen and phosphorus) is given body.The body functional group that gives in A can be bonded in metal M with intermolecular or intramolecularly mode
AOn.The body of giving in A preferably is bonded on the M in the intramolecularly mode.Possible is the no electric charge functional group of element of containing 15 or 16 families of the periodic table of elements to body, amine for example, imines, carboxylic acid amides, carboxylicesters; ketone (oxo), ether, thioketones, phosphine; phosphorous acid ester, phosphine oxide, alkylsulfonyl, sulphonamide or unsubstituted, replacement or condensed heterocycle system.A being connected on cyclopentadienyl group and Z can be by for example synthesizing with the similar method of describing in WO 00/35928 of method.
A preferably is selected from following group in these :-OR
13A-,-SR
13A-,-NR
13AR
14A-,-PR
13AR
14A-,-C=NR
13A-and unsubstituted, replacement or condensed heteroaromatic rings system, especially-NR
13AR
14A-,-C=NR
13A-and unsubstituted, replacement or condensed heteroaromatic rings system.
R
13AAnd R
14ABe hydrogen separately independently of one another, linearity or branching C
1-C
20-alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, (it can and then carry C to 5-to the first cycloalkyl of 7-
6-C
10-aryl is as substituting group), for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, C
2-C
20-alkenyl (it can be linear, and keys ring-type or branching and wherein two can be inner or terminal), vinyl for example, 1-allyl group, 2-allyl group, the 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, C
6-C
20-aryl (it can be replaced by other alkyl), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2,6-dimethyl benzene-1-base, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-Three methyl Benzene-1-base, the alkylaryl that in moieties, has 1-10 carbon atom and in aryl moiety, have 6-20 carbon atom and can be replaced by other alkyl, benzyl for example, adjacent-, between-, right-methyl-benzyl, 1-or 2-ethylphenyl or SiR
15A 3, this organic radical R wherein
13A-R
14AAlso can be by halogen such as fluorine, chlorine or bromine or nitrogenous group and other C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and have the alkylaryl or the SiR of 6-20 carbon atom in aryl moiety in moieties
15A 3Group replaces and two ortho position radicals R
13A-R
14AAlso can link to each other and form five-or six-ring and this radicals R
15ABe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl or 1～10 carbon atom is arranged and alkylaryl and two radicals R of 6～20 carbon atoms are arranged at aryl moiety at moieties
15AAlso can link to each other and form five-or six-unit ring.
NR
13AR
14AIt is amide substituents.It is secondary amide preferably, as dimethylformamide, and the N-ethylmethyl amide, diethylamide, N-methyl-propyl acid amides, N-isopropyl methyl acid amides, N-ethyl sec.-propyl acid amides, dipropyl acid amides, diisopropylamide, N-methyl butyl acid amides, N-ethyl-butyl acid amides, N-methyl-tert-butylamides, the N-te t-butylisopropylamide, dibutyl acid amides, two-sec-butyl acid amides, the diisobutyl acid amides, tert-pentyl-tert-butylamides, diamyl acid amides, N-methyl hexyl acid amides, dihexyl acid amides, tert-pentyl-uncle's octyl group acid amides, the dioctyl acid amides, two (2-ethylhexyl) acid amides, didecyl acid amides, N-methyl octadecyl acid amides, N-methyl-cyclohexyl base acid amides, N-ethyl cyclohexyl amide, N-isopropylcyclohexyl-acid amides, N-tert-butylcyclohexyl acid amides, the dicyclohexyl acid amides, tetramethyleneimine, piperidines, hexamethylene imine, decahydroquinoline, pentanoic, N-methyl anilide (methylanilide) or N-ethyl anilide (ethylanilide).
At this imino--C=NR
13AIn, R
13AC preferably
6-C
20-aryl (it can be replaced by other alkyl), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2,6-dimethyl benzene-1-base, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-Three methyl Benzene-1-base.
A preferably can also contain heteroatomic unsubstituted, replacement or the condensed heteroaromatic rings system that is selected from oxygen, sulphur, nitrogen and the phosphorus except encircling carbon atom.Also can contain the example that 1-4 nitrogen-atoms or 1-3 nitrogen-atoms and/or sulphur or Sauerstoffatom go up member's 5-unit heteroaryl as ring except carbon atom is the 2-furyl, 2-thienyl, 2-pyrryl, the 3-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, the 5-isothiazolyl, 1-pyrazolyl, 3-pyrazolyl, the 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, the 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, the 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, the 5-imidazolyl, 1,2,4-oxadiazole-3-base, 1,2,4-oxadiazole-5-base, 1,3,4-oxadiazole-2-base and 1,2,4-triazole-3-base.The example that can contain the 6-unit heteroaryl of 1-4 nitrogen-atoms and/or phosphorus atom is the 2-pyridyl, 2-phospha phenyl, 3-pyridazinyl, 2-pyrimidyl, 4-pyrimidyl, 2-pyrazinyl, 1,3,5-triazines-2-base and 1,2,4-triazine-3-base, 1,2,4-triazine-5-base and 1,2,4-triazine-6-base.This 5-person and 6-unit heteroaryl also can be by C
1-C
10-alkyl, C
6-C
10-aryl has 1-10 carbon atom and have the alkylaryl of 6-10 carbon atom in aryl moiety in moieties, trialkylsilkl or halogen such as fluorine, chlorine or bromine replace or condense with one or more aromatics or heteroaromatic rings.The example of the first heteroaryl of benzo-fused 5-is the 2-indyl, 7-indyl, 2-benzofuryl, 7-benzofuryl, 2-sulfo-naphthyl, 7-sulfo-naphthyl, 3-indazolyl, 7-indazolyl, 2-benzimidazolyl-and 7-benzimidazolyl-.The example of the first heteroaryl of benzo-fused 6-is the 2-quinolyl, 8-quinolyl, 3-cinnolines base, 8-cinnolines base, 1-phthalazinyl, 2-quinazolyl, 4-quinazolyl, 8-quinazolyl, 5-quinoxalinyl, 4-acridyl, 1-phenanthridinyl and 1-phenazinyl.The heterocyclic naming ﹠ numbering derives from L.Fieser andM.Fieser, Lehrbuch der organischen Chemie, and the 3rd revised edition, VerlagChemie, Weinheim 1957.
Among these heteroaromatic system A, particularly preferably be in heteroaromatic moiety, have 1,2,3,4 or 5 nitrogen-atoms unsubstituted, replace and/or the hexa-atomic heteroaromatic rings of condensed, especially replace with unsubstituted 2-pyridyl or 2-quinolyl.A is the group of preferably following general formula (IV) therefore
Wherein
E
6A-E
9ABe carbon or nitrogen separately independently of one another,
R
16A-R
19ABe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and have the alkylaryl or the SiR of 6-20 carbon atom in aryl moiety in moieties
20A 3, this organic radical R wherein
16A-R
19AAlso by halogen or nitrogen and other C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and have the alkylaryl or the SiR of 6-20 carbon atom in aryl moiety in moieties
20A 3Replace and two ortho position radicals R
16A-R
19AOr R
16AAlso can link to each other with Z form five-or six-ring and
Radicals R
20ABe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl or in alkyl, have 1 to 10 carbon atom and in aryl, have alkylaryl and two radicals R of 6-20 carbon atom
20AAlso can link to each other form five-or six-ring and
P is at E
6A-E
9ABe 0 and when being nitrogen at E
6A-E
9ABe 1 when being carbon.
Especially, E
6A-E
9ABe nitrogen and all the other when being carbon p be 0 or 1.A is the 2-pyridyl especially preferably, 6-methyl-2-pyridyl, 4-methyl-2-pyridyl, 5-methyl-2-pyridyl, 5-ethyl-2-pyridyl, 4,6-dimethyl-2-pyridyl, the 3-pyridazinyl, 4-pyrimidyl, 2-pyrazinyl, 6-methyl-2-pyrazinyl, 5-methyl-2-pyrazinyl, 3-methyl-2-pyrazinyl, 3-ethyl pyrazine base, 3,5,6-trimethylammonium-2-pyrazinyl, 2-quinolyl, 4-methyl-2-quinolyl, 6-methyl-2-quinolyl, 7-methyl-2-quinolyl, 2-quinoxalinyl or 3-methyl-2-quinoxalinyl.
Because the easiness of preparation, the preferably combination of Z and A is more such, wherein Z be unsubstituted or replace 1,2-phenylene and A are NR
16AR
17AAnd more like this, wherein Z is-CHR
6A-,-CH
2-,-C (CH
3)
2Or-Si (CH
3)
2-and A be unsubstituted or the 2-quinolyl or the 2-pyridyl unsubstituted or that replace that replace.Wherein k is that 0 the system that does not have abutment Z is synthetic also simple very especially.The preferably unsubstituted or 8-quinolyl that replaces of A in this case.In addition, when k is 0, R
2AC preferably
6-C
22-aryl or in moieties, have 1-10 carbon atom and in aryl moiety, have the alkylaryl of 6-20 carbon atom, preferred C
6-C
22-aryl such as phenyl, naphthyl, xenyl, anthryl or phenanthryl, wherein this aryl also can be contained N-, P-, the substituting group of O-or S-, C
1-C
22-alkyl, C
2-C
22-alkenyl, halogen or haloalkyl or halogen aryl with 1-10 carbon atom replace.
More than also be preferred in these preferably make up for the described preferred embodiment of variable.
M
ABe to be selected from titanium (being in oxidation state 3), vanadium, chromium, the metal in molybdenum and the tungsten, preferred titanium (being in oxidation state 3) and chromium.Particularly preferably be and be in oxidation state 2,3 and 4, especially 3 chromium.Metal complexes, especially chromic compound can pass through suitable metal-salt, and for example metal chloride obtains (for example by use and the similar method of embodiment in DE 19710615) with the ligand anionic reactive with plain mode.
Among suitable monocyclopentadienyl title complex (A1), general formula Cp-Y preferably
mM
AX
n(V) those, wherein variable Cp, Y, A, m and M
AAs defined above with their preferred embodiment here also be preferred and:
X
ABe fluorine separately independently of one another, chlorine, bromine, iodine, hydrogen, C
1-C
10-alkyl, C
2-C
10-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, NR in moieties
21AR
22A, OR
21A, SR
21A, SO
3R
21A, OC (O) R
21A, CN, SCN, beta-diketon root (beta-diketonate), CO, BF
4 -, PF
6 -Or huge non-coordination anion or two radicals X
AThat form to replace or unsubstituted diene ligand, especially 1,3-diene ligand and this radicals X
ACan be connected with each other,
R
21A-R
22ABe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, SiR in moieties
23A 3, this organic radical R wherein
21A-R
22AAlso can by halogen or nitrogenous-and oxygen containing group replace and two radicals R
21A-R
22AAlso can link to each other forms five-or six-ring,
Radicals R
23ABe hydrogen separately independently of one another, C
1-C
20-alkyl, CX-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and have alkylaryl and two radicals R of 6-20 carbon atom in aryl moiety in moieties
23AAlso can link to each other form five-or six-ring and
N is 1,2, or 3.
More than for Cp, Y, Z, A, m and M
AExample and the preferred embodiment described are applicable to these preferred monocyclopentadienyl title complexs equally individually and in combination.
Ligand X
AFor example derive from the selection of the synthetic suitable initial metallic compound that is used for the monocyclopentadienyl title complex, but also can be in change afterwards.Possible ligand X
AEspecially halogen such as fluorine, chlorine, bromine or iodine, special chlorine.Alkyl such as methyl, ethyl, propyl group, butyl, vinyl, allyl group, phenyl or benzyl also are ideal ligand X
ACan mention, purely for example and but other ligand X of enumerating exhaustively anything but
ABe the trifluoroacetic acid root, BF
4 -, PF
6 -With weak coordinate or non-coordinate negatively charged ion (referring to, S.Strauss in Chem.Rev.1993 for example, 93,927-942), B (C for example
6F
5)
4 -
Acid amides,-oxyl, sulfonate radical, carboxylate radical and beta-diketon root also are useful especially ligand X
ARadicals R
21AAnd R
22AVariation for example make physicals such as solubleness to regulate subtly.Possible carbon organic substituent R
21A-R
22ABe following groups for example: the C of linearity or branching
1-C
20-alkyl, methyl for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, (it can and then carry C to 5-to the first cycloalkyl of 7-
6-C
10-aryl is as substituting group), cyclopropyl for example, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, C
2-C
20-alkenyl (it can be linear, and keys ring-type or branching and wherein two can be inner or terminal), vinyl for example, 1-allyl group, 2-allyl group, the 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, C
6-C
20-aryl (it can and/or contain N-or the group of O-replaces by other alkyl), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2, the 6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl, 2-p-methoxy-phenyl, 2-N, N-dimethylamino phenyl or arylalkyl, wherein arylalkyl can be replaced by other alkyl, benzyl for example, adjacent-, between-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein R
21AAlso can be connected to R
22AForm 5-or 6-unit ring and this organic radical R
21A-R
22AAlso can be by halogen such as fluorine, chlorine or bromine replaces.At organosilicon substituting group SiR
23A 3In possible radicals R
23ABe for R with above
21A-R
22AMentioned identical group, wherein two R
23AAlso can link to each other and form 5-or 6-unit ring, for example trimethyl silyl, triethylsilyl, butyl dimetylsilyl, tributyl silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.Preferably use C
1-C
10-alkyl such as methyl, ethyl, n-propyl, normal-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and vinyl, allyl group, benzyl and phenyl are as radicals R
21AAnd R
22AAmong the ligand X of these replacements some are preferred especially uses, because they can obtain from starting raw material cheap and that be purchased easily.Therefore, particularly preferred example is X wherein
ABe dimethylformamide, methoxyl group, oxyethyl group, isopropoxy, phenoxy group, naphthyloxy, the trifluoromethanesulfonic acid root, right-tosylate, those of acetate moiety or methyl ethyl diketone acid group.
Ligand X
ANumber n depend on transition metal M
AOxidation state.Therefore this number n does not briefly provide.Transition metal M in the catalytic activity title complex
AOxidation state normally those in this area are known to the skilled.Chromium, molybdenum and tungsten probably exist with oxidation state+3, vanadium with oxidation state+3 or+4 exist.Yet, also might use such title complex, its oxidation state does not correspond to the oxidation state of active catalyst.This type of title complex can suitably reduce or oxidation by enough suitable activators then.Preferably use chromic compound that is in oxidation state+3 and the titanium complex that is in oxidation state 3.
The preferred monocyclopentadienyl title complex (A1) of this type is that dichloro 1-(8-quinolyl)-3-benzyl ring pentadienyl closes chromium (III), dichloro 1-(8-quinolyl)-3-(1-naphthyl) cyclopentadienyl closes chromium (III), dichloro 1-(8-quinolyl)-3-(4-trifluoromethyl) cyclopentadienyl closes chromium (III), dichloro 1-(8-quinolyl)-2-methyl-3-benzyl ring pentadienyl closes chromium (III), dichloro 1-(8-quinolyl)-2-methyl-3-(1-naphthyl) cyclopentadienyl closes chromium (III), dichloro 1-(8-quinolyl)-2-methyl-3-(4-trifluoromethyl) cyclopentadienyl closes chromium (III), dichloro 1-(8-quinolyl)-2-phenyl indenyl closes chromium (III), dichloro 1-(8-quinolyl)-2-phenyl benzo indenyl closes chromium (III), dichloro 1-(8-(2-toluquinoline base))-2-methyl-3-benzyl ring pentadienyl closes chromium (III), dichloro 1-(8-(2-toluquinoline base))-2-phenyl indenyl closes chromium (III), dichloro 1-(2-pyridylmethyl)-3-benzyl ring pentadienyl closes chromium (III), dichloro 1-(2-pyridylmethyl)-2-methyl-3-benzyl ring pentadienyl closes chromium (III), dichloro 1-(2-quinolyl methyl)-3-benzyl ring pentadienyl closes chromium, dichloro 1-(2-pyridyl ethyl)-3-benzyl ring pentadienyl closes chromium, dichloro 1-(2-pyridyl-1-methylethyl)-3-benzyl ring pentadienyl closes chromium, dichloro 1-(2-pyridyl-1-phenyl methyl)-3-benzyl ring pentadienyl closes chromium, dichloro 1-(2-pyridylmethyl) indenyl closes chromium (III), dichloro 1-(2-quinolyl methyl) indenyl closes chromium, dichloro 1-(2-pyridyl ethyl) indenyl closes chromium, dichloro 1-(2-pyridyl-1-methylethyl) indenyl closes chromium, dichloro 1-(2-pyridyl-1-phenyl methyl) indenyl closes chromium, dichloro 5-[(2-pyridyl) methyl]-1,2,3,4-tetramethyl-ring pentadienyl closes chromium and dichloro 1-(8-(2-toluquinoline base))-2-methyl benzo indenyl closes chromium (III).
The preparation of this type of functionalized cyclopentadienyl ligand is known.These cooperate the various synthetic routes with ligand to be described in Chem.Ber. (1996) by people such as for example M.Enders, and 129,459-463 or P.Jutzi and U.Siemeling are described in J.Orgmet.Chem. (1995), and 500, among the 175-185.
The synthetic of this type of title complex can be undertaken by known method itself, and wherein the cyclic hydrocarbon negatively charged ion that suitably replaces and the halid reaction of titanium, vanadium or chromium are preferred.The example of appropriate preparation method has been described in for example Journal of Organometallic Chemistry, and 369 (1989), among the 359-370 and in EP-A-1212333.
Specially suitable luxuriant hafnium (A2) is the hafnium complexes of general formula (VI)
Wherein substituting group and subscript have following meanings:
X
BBe fluorine, chlorine, bromine, iodine, hydrogen, C
1-C
10-alkyl, C
2-C
10-alkenyl, C
6-C
15-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety ,-OR in moieties
6BOr-NR
6BR
7B, or two radicals X
BThat form to replace or unsubstituted diene ligand, especially 1,3-diene ligand, and this radicals X
BBe identical or different and can be connected with each other,
E
1B-E
5BEach is a carbon or a no more than E naturally
1B-E
5BBe phosphorus or nitrogen, preferred carbon,
T is 1,2 or 3 and depend on and the valence state of Hf make that the metallocene complex of general formula (VI) is uncharged,
Wherein
R
6BAnd R
7BEach is C naturally
1-C
10-alkyl, C
6-C
15-aryl has 1-10 carbon atom and have the alkylaryl of 6-20 carbon atom in aryl moiety in each comfortable moieties, arylalkyl, fluoroalkyl or fluoro aryl and
R
1B-R
5BBe hydrogen separately independently of one another, C
1-C
22-alkyl, 5-is to 7-unit cycloalkyl or cycloalkenyl group (it and then portability C
1-C
10Alkyl is as substituting group), C
2-C
22-alkenyl, C
6-C
22-aryl has 1-16 carbon atom and has the arylalkyl of 6-21 carbon atom in aryl moiety, NR in moieties
8B 2, N (SiR
8B 3)
2, OR
8B, OSiR
8B 3, SiR
8B 3, this organic radical R wherein
1B-R
5BAlso can be replaced and/or two radicals R by halogen
1B-R
5B, ortho position group especially, also can link to each other form five-, six-or seven-membered ring, and/or two ortho position radicals R
1D-R
5DCan link to each other form contain five of at least one atom of being selected among N, P, O and the S-, six-or seven-first heterocycle, wherein
Radicals R
8BCan be identical or different and can each C naturally
1-C
10-alkyl, C
3-C
10-cycloalkyl, C
6-C
15-aryl, C
1-C
4-alkoxyl group or C
6-C
10-aryloxy and Z
1BBe X
BOr
Group wherein
R
9B-R
13BBe hydrogen separately independently of one another, C
1-C
22-alkyl, 5-is to 7-unit cycloalkyl or cycloalkenyl group (it and then portability C
1-C
10Alkyl is as substituting group), C
2-C
22-alkenyl, C
6-C
22-aryl has 1-16 carbon atom and has the arylalkyl of 6-21 carbon atom in aryl moiety, NR in moieties
14B 2, N (SiR
14B 3)
2, OR
14B, OSiR
14B 3, SiR
14B 3, this organic radical R wherein
9B-R
13BAlso can be replaced and/or two radicals R by halogen
9B-R
13B, ortho position group especially, also can link to each other form five-, six-or seven-membered ring, and/or two ortho position radicals R
9B-R
13BCan link to each other to form to contain is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle, wherein
Radicals R
14BBe identical or different and each C naturally
1-C
10-alkyl, C
3-C
10-cycloalkyl, C
6-C
15-aryl, C
1-C
4-alkoxyl group or C
6-C
10-aryloxy,
E
6B-E
10BEach is a carbon or a no more than E naturally
6B-E
10BBe phosphorus or nitrogen, preferred carbon,
Or radicals R wherein
4BAnd Z
1BFormation-R together
15BV-A
1B-group, wherein
R
15BBe
=BR
16B,=BNR
16BR
17B,=AIR
16B,-Ge-,-Sn-,-O-,-S-,=SO ,=SO
2,=NR
16B,=CO ,=PR
16BOr=P (O) R
16B,
Wherein
R
16B-R
21BBe identical or different and each hydrogen atom naturally, halogen atom, trimethyl silyl, C
1-C
10-alkyl, C
1-C
10-fluoroalkyl, C
6-C
10-fluoro aryl, C
6-C
10-aryl, C
1-C
10-alkoxyl group, C
7-C
15-alkyl-aryloxy, C
2-C
10-alkenyl, C
7-C
40-arylalkyl, C
8-C
40-aromatic yl alkenyl or C
7-C
40-alkylaryl or two adjacent groups with the atom that connects them form saturated or unsaturated ring with 4-15 carbon atom and
M
2B-M
4BEach is silicon naturally, germanium or tin, or preferred silicon,
A
1BBe-O-,-S-,
=O ,=S ,=NR
22B,-O-R
22B,
-NR
22B 2,-PR
22B 2Or unsubstituted, replacement or the condensed heterocycle system, wherein
Radicals R
22BBe C separately independently of one another
1-C
10Alkyl, C
6-C
15-aryl, C
3-C
10-cycloalkyl, C
7-C
18-alkylaryl or Si (R
23B)
3,
R
23BBe hydrogen, C
1-C
10-alkyl, C
6-C
15(it can and then carry C to-aryl
1-C
4-alkyl is as substituting group) or C
3-C
10-cycloalkyl,
V is 1 or works as A
1BWhen being unsubstituted, replacement or condensed heterocycle system also can be 0
Or radicals R wherein
4BAnd R
12BFormation-R together
15B-group.
A
1BCan be for example and this bridged group R
15BForm amine together, ether, thioether or phosphine.Yet, A
1BAlso can be unsubstituted, replace or condensed heterocycle aromatic ring system, they can contain the heteroatoms in oxygen, sulphur, nitrogen and the phosphorus of being selected from except encircling carbon atom.Can also contain 1-4 nitrogen-atoms and/or sulphur or Sauerstoffatom except carbon atom is the 2-furyl as the example of the 5-of ring members unit heteroaryl, 2-thienyl, 2-pyrryl, the 3-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, the 5-isothiazolyl, 1-pyrazolyl, 3-pyrazolyl, the 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, the 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, the 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, the 5-imidazolyl, 1,2,4-oxadiazole-3-base, 1,2,4-oxadiazole-5-base, 1,3,4-oxadiazole-2-base and 1,2,4-triazole-3-base.The example that can contain the 6-unit heteroaryl of 1-4 nitrogen-atoms and/or phosphorus atom is the 2-pyridyl, 2-phospha phenyl, 3-pyridazinyl, 2-pyrimidyl, 4-pyrimidyl, 2-pyrazinyl, 1,3,5-triazines-2-base and 1,2,4-triazine-3-base, 1,2,4-triazine-5-base and 1,2,4-triazine-6-base.This 5-unit and 6-unit heteroaryl also can be by C
1-C
10-alkyl, C
6-C
10-aryl has 1-10 carbon atom and have the alkylaryl of 6-10 carbon atom in aryl moiety in moieties, trialkylsilkl or halogen such as fluorine, chlorine or bromine replace or condense with one or more aromatics or heteroaromatic rings.The example of the first heteroaryl of benzo-fused 5-is the 2-indyl, 7-indyl, 2-benzofuryl, 7-benzofuryl, 2-sulfo-naphthyl, 7-sulfo-naphthyl, 3-indazolyl, 7-indazolyl, 2-benzimidazolyl-and 7-benzimidazolyl-.The example of the first heteroaryl of benzo-fused 6-is the 2-quinolyl, 8-quinolyl, 3-cinnolines base, 8-cinnolines base, 1-phthalazinyl, 2-quinazolyl, 4-quinazolyl, 8-quinazolyl, 5-quinoxalinyl, 4-acridyl, 1-phenanthridinyl and 1-phenazinyl.The heterocyclic naming ﹠ numbering derives from L.Fieser and M.Fieser, Lehrbuch der organischen Chemie, and the 3rd revised edition, Verlag Chemie, Weinheim 1957.
Radicals X in general formula (XIV)
BChoosing is identical, preferred fluorine, chlorine, bromine, C
1-C
7-alkyl or aralkyl, especially chlorine, methyl or benzyl.
The synthetic of this type of title complex can be undertaken by known method itself, and wherein the cyclic hydrocarbon negatively charged ion that suitably replaces and the halid reaction of hafnium are preferred.The example of appropriate preparation method has been described in for example Journal of Organometallic Chemistry, and 369 (1989), among the 359-370.
Luxuriant hafnium can or be intended racemize (pseudo-Rac) form and use with racemize (Rac).This term is intended racemize and is referred to such title complex, and wherein two cyclopentadienyl ligands are arranged by racemize each other when whole other substituting groups of title complex are ignored.
The example of suitable luxuriant hafnium (A2) is, especially,
Dichloro methylene-bis (cyclopentadienyl) closes hafnium, dichloro methylene-bis (3-methyl cyclopentadienyl) closes hafnium, dichloro methylene-bis (3-n-butyl cyclopentadienyl) closes hafnium, dichloro methylene-bis (indenyl) closes hafnium, dichloro methylene-bis (tetrahydro indenyl) closes hafnium, dichloro isopropylidene two (cyclopentadienyl) closes hafnium, dichloro isopropylidene two (3-trimethyl silyl cyclopentadienyl) closes hafnium, dichloro isopropylidene two (3-methyl cyclopentadienyl) closes hafnium, dichloro isopropylidene two (3-n-butyl cyclopentadienyl) closes hafnium, dichloro isopropylidene two (3-benzyl ring pentadienyl) closes hafnium, dichloro isopropylidene two (indenyl) closes hafnium, dichloro isopropylidene two (tetrahydro indenyl) closes hafnium, dichlorodimethylsilane two bases two (cyclopentadienyl) close hafnium, dichlorodimethylsilane two bases two (indenyl) close hafnium, dichlorodimethylsilane two bases two (tetrahydro indenyl) close hafnium, dichloro ethylenebis (cyclopentadienyl) is closed hafnium, dichloro ethylenebis (indenyl) is closed hafnium, dichloro ethylenebis (tetrahydro indenyl) is closed hafnium, dichloro tetramethyl-ethylidene-9-fluorenyl cyclopentadiene base closes hafnium, dichlorodimethylsilane two bases two (tetramethyl-ring pentadienyl) close hafnium, dichlorodimethylsilane two bases two (3-trimethyl silyl cyclopentadienyl) close hafnium, dichlorodimethylsilane two bases two (3-methyl cyclopentadienyl) close hafnium, dichlorodimethylsilane two bases two (3-n-butyl cyclopentadienyl) close hafnium, dichlorodimethylsilane two bases two (the 3-tertiary butyl-5-methyl cyclopentadienyl) close hafnium, dichlorodimethylsilane two bases two (the 3-tertiary butyl-5-ethyl cyclopentadienyl) close hafnium, dichlorodimethylsilane two bases two (2-methyl indenyl) close hafnium, dichlorodimethylsilane two bases two (2-sec.-propyl indenyl) close hafnium, dichlorodimethylsilane two bases two (2-tertiary butyl indenyl) close hafnium, dibromo diethylsilane two bases two (2-methyl indenyl) close hafnium, dichlorodimethylsilane two bases two (3-methyl-5-methyl cyclopentadienyl) close hafnium, dichlorodimethylsilane two bases two (3-ethyl-5-sec.-propyl cyclopentadienyl) close hafnium, and dichlorodimethylsilane two bases two (2-ethyl-indenyl) close hafnium, two (the 2-methyl-4 of dichlorodimethylsilane two bases, 5-benzo indenyl) closes hafnium, dichlorodimethylsilane two bases two (2-ethyl-4,5-benzo indenyl) close hafnium, two (the 2-methyl-4 of dichloromethyl phenyl silane two bases, 5-benzo indenyl) closes hafnium, dichloromethyl phenyl silane two bases two (2-ethyl-4,5-benzo indenyl) close hafnium, two (the 2-methyl-4 of dichloro diphenyl silane two bases, 5-benzo indenyl) closes hafnium, dichloro diphenyl silane two bases two (2-ethyl-4,5-benzo indenyl) close hafnium, and dichloro diphenyl silane two bases two (2-methyl indenyl) close hafnium, dichlorodimethylsilane two bases two (2-methyl-4-phenyl indenyl) close hafnium, dichlorodimethylsilane two bases two (2-ethyl-4-phenyl indenyl) close hafnium, and dichlorodimethylsilane two bases two (2-methyl-4-(1-naphthyl) indenyl) close hafnium, and dichlorodimethylsilane two bases two (2-ethyl-4-(1-naphthyl) indenyl) close hafnium, dichlorodimethylsilane two bases two (2-propyl group-4-(1-naphthyl) indenyl) close hafnium, dichlorodimethylsilane two bases two (2-isobutyl--4-(1-naphthyl) indenyl) close hafnium, and dichlorodimethylsilane two bases two (2-propyl group-4-(9-phenanthryl) indenyl) close hafnium, and dichlorodimethylsilane two bases two (2-methyl-4-sec.-propyl indenyl) close hafnium, dichlorodimethylsilane two bases two (2,7-dimethyl-4-sec.-propyl indenyl) close hafnium, dichlorodimethylsilane two bases two (2-methyl-4,6-di-isopropyl indenyl) close hafnium, dichlorodimethylsilane two base two (2-methyl-4-[is right-trifluoromethyl] indenyl) closes hafnium, dichlorodimethylsilane two base two (2-methyl-4-[3 ', 5 '-3,5-dimethylphenyls] indenyl) closes hafnium, and dichlorodimethylsilane two bases two (2-methyl-4-[4 '-tert-butyl-phenyl] indenyl) close hafnium, dichloro-diethyl silane two base two (2-methyl-4-[4 '-tert-butyl-phenyl] indenyl) closes hafnium, dichlorodimethylsilane two base two (2-ethyl-4-[4 '-tert-butyl-phenyl] indenyl) closes hafnium, and dichlorodimethylsilane two bases two (2-propyl group-4-[4 '-tert-butyl-phenyl] indenyl) close hafnium, and dichlorodimethylsilane two bases two (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl) close hafnium, dichlorodimethylsilane two bases (2-sec.-propyl-4-phenyl indenyl) (2-methyl-4-phenyl indenyl) close hafnium, dichlorodimethylsilane two bases (2-sec.-propyl-4-(1-naphthyl) indenyl) (2-methyl-4-(1-naphthyl) indenyl) close hafnium, and dichlorodimethylsilane two bases (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl) (2-methyl-4-[4 '-tert-butyl-phenyl] indenyl) close hafnium, and dichlorodimethylsilane two bases (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl) (2-methyl-4-[1 '-naphthyl] indenyl) close hafnium and two chlorethylidenes (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl) (2-methyl-4-[4 '-tert-butyl-phenyl] indenyl) and close hafnium, with corresponding dimethyl hafnium, monochloro list (alkyl-aryloxy) hafnium and two (alkyl-aryloxy) hafnium compound.This title complex can be with racemic form, meso-form or use as both forms of mixture.
Among the luxuriant hafnium of general formula (VI), those of general formula (VII)
Be preferred.
Among the compound of general formula (VII), preferably such compounds, wherein
X
BBe fluorine, chlorine, bromine, C
1-C
4Alkyl or benzyl, or two radicals X
BForm that replace or unsubstituted divinyl ligand,
T is 1 or 2, and is preferred 2,
R
1B-R
5BEach is hydrogen naturally, C
1-C
8-alkyl, C
6-C
8-aryl, NR
8B 2, OSiR
8B 3Or Si (R
8B)
3With
R
9B-R
13BEach is hydrogen naturally, C
1-C
8-alkyl or C
6-C
8-aryl, NR
14B 2, OSiR
14B 3Or Si (R
14B)
3
Or under each situation two radicals R
1B-R
5BAnd/or R
9B-R
13BWith C
5Ring forms indenyl, the indenyl of fluorenyl or replacement or fluorenyl systems together.
Wherein cyclopentadienyl group is that the luxuriant hafnium of identical general formula (VII) is useful especially.
The special suitable combination thing D of general formula (VII)) example is, especially:
Dichloro two (cyclopentadienyl) closes hafnium, dichloro two (indenyl) closes hafnium, dichloro two (fluorenyl) closes hafnium, dichloro two (tetrahydro indenyl) closes hafnium, dichloro two (pentamethyl-cyclopentadienyl) closes hafnium, dichloro two (trimethyl silyl cyclopentadienyl) closes hafnium, dichloro two (trimethoxysilyl cyclopentadienyl) closes hafnium, dichloro two (ethyl cyclopentadienyl) closes hafnium, dichloro two (isobutyl-cyclopentadienyl) closes hafnium, dichloro two (3-butenyl cyclopentadienyl) closes hafnium, dichloro two (methyl cyclopentadienyl) closes hafnium, dichloro two (1,3-two-tertiary butyl cyclopentadienyl) closes hafnium, dichloro two (trifluoromethyl cyclopentadienyl) closes hafnium, dichloro two (tertiary butyl cyclopentadienyl) closes hafnium, dichloro two (n-butyl cyclopentadienyl) closes hafnium, dichloro two (benzyl ring pentadienyl) closes hafnium, two (the N of dichloro, N-dimethylaminomethyl cyclopentadienyl) closes hafnium, dichloro two (1,3-dimethyl cyclopentadienyl) closes hafnium, dichloro two (1-normal-butyl-3-methyl cyclopentadienyl) closes hafnium, dichloro (cyclopentadienyl) (methyl cyclopentadienyl) closes hafnium, dichloro (cyclopentadienyl) (n-butyl cyclopentadienyl) closes hafnium, dichloro (methyl cyclopentadienyl) (n-butyl cyclopentadienyl) closes hafnium, two chloro-(cyclopentadienyl) (1-methyl-3-n-butyl cyclopentadienyl) close hafnium, and dichloro two (tetramethyl-ring pentadienyl) closes hafnium and corresponding dimethyl hafnium compound.Other example is corresponding luxuriant hafnium compound, and wherein one or two in the chlorine root ligand substituted by bromine root or iodine root.
Appropriate catalyst B) be transition metal complex with at least a ligand of general formula X V-XIX,
Wherein variable has following meanings:
E
1CBe nitrogen or phosphorus, nitrogen especially,
E
2C-E
4CBe carbon separately independently of one another, nitrogen or phosphorus, carbon especially,
R
1C-R
3CBe hydrogen separately independently of one another, C
1-C
22-alkyl, C
2-C
22-alkenyl, C
6-C
22-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, halogen, NR in moieties
18C 2, OR
18C, SiR
19C 3, this organic radical R wherein
1C-R
3CAlso can be replaced and/or two ortho position radicals R by halogen
1C-R
3CAlso can link to each other form five-, six-or seven-membered ring, and/or two ortho position radicals R
1C-R
3CContinuous formation contains and is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle,
R
4C-R
7CBe hydrogen separately independently of one another, C
1-C
22-alkyl, C
2-C
22-alkenyl, C
6-C
22-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, NR in moieties
18C 2, SiR
19C 3, this organic radical R wherein
4C-R
7CAlso can be replaced and/or two paired or adjacent radicals R by halogen
4C-R
7CAlso can link to each other form five-, six-or seven-membered ring, and/or two paired or adjacent radicals R
4C-R
9CContinuous formation contains and is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle, and when v is 0, R
6CBe to be connected to L
1CKey and/or R
7CBe to be connected to L
2CKey, L like this
1CFormed to be connected to and carried R
4CCarbon atom on two keys and/or L
2CFormed to be connected to and carried R
5CCarbon atom on two keys,
U is at E
2C-E
4CBe 0 and when being nitrogen or phosphorus at E
2C-E
4CBe 1 when being carbon,
L
1C-L
2CBe nitrogen or phosphorus separately independently of one another, nitrogen especially,
R
8C-R
11CBe C separately independently of one another
1-C
22-alkyl, C
2-C
22-alkenyl, C
6-C
22-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, halogen, NR in moieties
18C 2, OR
18C, SiR
19C 3, this organic radical R wherein
8C-R
11CAlso can be replaced and/or two ortho position radicals R by halogen
8C-R
17CAlso can link to each other form five-, six-or seven-membered ring, and/or two ortho position radicals R
8C-R
17CContinuous formation contains and is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle,
R
12C-R
17CBe hydrogen separately independently of one another, C
1-C
22-alkyl, C
2-C
22-alkenyl, C
6-C
22-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, halogen, NR in moieties
18C 2, OR
18C, SiR
19C 3, this organic radical R wherein
12C-R
17CAlso can be replaced and/or two ortho position radicals R by halogen
8C-R
17CAlso can link to each other form five-, six-or seven-membered ring, and/or two ortho position radicals R
8C-R
17CContinuous formation contains and is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle,
Subscript v is 0 or 1 separately independently of one another,
Radicals X
CBe fluorine separately independently of one another, chlorine, bromine, iodine, hydrogen, C
1-C
10-alkyl, C
2-C
10-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, NR in moieties
18C 2, OR
18C, SR
18C, SO
3R
18C, OC (O) R
18C, CN, SCN, beta-diketon root, CO, BF
4 -, PF
6 -Or huge non-coordination anion and this radicals X
CCan be connected to each other,
Radicals R
18CBe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, SiR in moieties
19C 3, this organic radical R wherein
18CAlso can be by halogen or nitrogenous-and replacement of oxygen containing group and two radicals R
18CAlso can link to each other forms five-or six-ring,
Radicals R
19CBe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and have the alkylaryl of 6-20 carbon atom in aryl moiety, wherein this organic radical R in moieties
19CAlso can be by halogen or nitrogenous-and replacement of oxygen containing group and two radicals R
19CAlso can link to each other forms five-or six-ring,
S is 1,2,3 or 4, especially 2 or 3,
D be no electric charge give body and
T is 0-4, especially 0,1 or 2.
Three atom E in molecule
2C-E
4CCan be identical or different.If E
1CBe phosphorus, E then
2C-E
4CPreferred each carbon naturally.If E
1CBe nitrogen, E then
2C-E
4CPreferably nitrogen or carbon, especially carbon separately.
Substituent R
1C-R
3CAnd R
8C-R
17CCan in wide region, change.Possible carbon organic substituent R
1C-R
3CAnd R
8C-R
17CBe following groups for example: the C of linearity or branching
1-C
22-alkyl, methyl for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, (it can and then carry C to 5-to the first cycloalkyl of 7-
1-C
10-alkyl and/or C
6-C
10-aryl is as substituting group), cyclopropyl for example, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, C
2-C
22-alkenyl (it can be linear, and keys ring-type or branching and wherein two can be inner or terminal), vinyl for example, 1-allyl group, 2-allyl group, the 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, C
6-C
22-aryl (it can be replaced by other alkyl), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2, the 6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl, or arylalkyl (it can be replaced by other alkyl), benzyl for example, adjacent-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein two radicals R
1C-R
3CAnd/or two ortho position radicals R
8C-R
17CAlso can link to each other forms 5-, 6-or 7-unit ring and/or ortho position radicals R
1C-R
3CIn two and/or ortho position radicals R
8C-R
17CIn two can link to each other to form to contain and be selected from N, P, five of at least one atom among O and the S-, six-or seven-first heterocycle and/or this organic radical R
1C-R
3CAnd/or R
8C-R
17CAlso can be by halogen such as fluorine, chlorine or bromine replaces.In addition, R
1C-R
3CAnd R
8C-R
17CAlso can be amino N R
18C 2Or N (SiR
19C 3)
2, alkoxyl group or aryloxy OR
18C, dimethylamino for example, N-pyrrolidyl, picolinyl, methoxyl group, oxyethyl group or isopropoxy or halogen such as fluorine, chlorine or bromine.At organosilicon substituting group SiR
19C 3In possible radicals R
19CBe for R with above
1C-R
3CDescribed identical carbon organic group, wherein two R
19CAlso can link to each other forms 5-or 6-unit ring, trimethyl silyl for example, triethylsilyl, the butyl dimetylsilyl, tributyl silyl, three-tertiary butyl silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.These SiR
19C 3Group also can be bonded in E via oxygen or nitrogen
2C-E
4C, for example trimethyl silyl oxygen base, triethylsilyl oxygen base, butyl dimetylsilyl oxygen base, tributyl silyl oxygen base or tri-tert silyl oxygen base.
Preferred radicals R
1C-R
3CBe hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, neighbour-dialkyl group-or the phenyl that replaces of-two chloro-, trialkyl-or three the chloro-phenyl, naphthyl, xenyl and the anthryl that replace.Particularly preferred organosilicon substituting group is the trialkylsilkl that has 1-10 carbon atom in alkyl, especially trimethyl silyl.
Preferred radicals R
12C-R
17CBe hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, fluorine, chlorine and bromine, especially hydrogen.Especially, R
13CAnd R
16CEach is methyl naturally, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, fluorine, chlorine or bromine and R
12C, R
14C, R
15CAnd R
14CEach is hydrogen naturally.
Preferred radicals R
8C-R
11CBe methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, fluorine, chlorine and bromine.Especially, R
8CAnd R
10CEach is C naturally
1-C
22-alkyl (it also can be replaced by halogen), especially C
1-C
22-positive alkyl (it also can be replaced by halogen), methyl for example, trifluoromethyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or halogen such as fluorine, chlorine or bromine and R
9CAnd R
11CEach is halogen such as fluorine naturally, chlorine or bromine.Particularly preferably be R
8CAnd R
10CRespectively be C
1-C
22-alkyl (it also can be replaced by halogen), especially C
1-C
22-positive alkyl (it also can be replaced by halogen), methyl for example, trifluoromethyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl and R
9CAnd R
11CEach is halogen such as fluorine naturally, chlorine or bromine.
Especially, R
12C, R
14C, R
15CAnd R
17CBe identical, R
13CAnd R
16CBe identical, R
9CAnd R
11CBe identical and R
8CAnd R
10CBe identical.This also is preferred in aforesaid preferred embodiment.
Substituent R
4C-R
7CIn wide region, change equally.Possible carbon organic substituent R
4C-R
7CBe following groups for example: the C of linearity or branching
1-C
22-alkyl, methyl for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, (it can and then carry C to 5-to the first cycloalkyl of 7-
1-C
10-alkyl and/or C
6-C
10-aryl is as substituting group), cyclopropyl for example, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, C
2-C
22-alkenyl (it can be linear, and keys ring-type or branching and wherein two can be inner or terminal), vinyl for example, 1-allyl group, 2-allyl group, the 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, C
6-C
22-aryl (it can be replaced by other alkyl), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2, the 6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl, or arylalkyl, wherein this arylalkyl can be replaced by other alkyl, benzyl for example, adjacent-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein two radicals R
4CTo R
7CAlso can link to each other forms 5-, 6-or 7-unit ring and/or two paired radicals R
4C-R
7CCan link to each other to form to contain is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle and/or this organic radical R
4C-R
7CAlso can be by halogen such as fluorine, chlorine or bromine replaces.In addition, R
4C-R
7CCan be amino N R
18C 2Or N (SiR
19C 3)
2, dimethylamino for example, N-pyrrolidyl or picolinyl.At organosilicon substituting group SiR
19C 3In possible radicals R
19CBe for R with above
1C-R
3CDescribed identical carbon organic group, wherein two R
19CAlso can link to each other forms 5-or 6-unit ring, trimethyl silyl for example, triethylsilyl, the butyl dimetylsilyl, tributyl silyl, three-tertiary butyl silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.These SiR
19C 3Group also can be keyed on the carbon that carries them via nitrogen.When v is 0, R
6CBe to be connected to L
1COn key and/or R
7CBe to be connected to L
2COn key, L like this
1CFormed to be connected to and carried R
4CCarbon atom on two keys and/or L
2CFormed to be connected to and carried R
5CCarbon atom on two keys.
Preferred radicals R
4C-R
7CBe hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, neighbour-dialkyl group-or the phenyl that replaces of two chloro-, trialkyl-or three the chloro-phenyl, naphthyl, xenyl and the anthryl that replace.Also amide substituents NR preferably
18C 2, secondary amide especially is as dimethylformamide, the N-ethylmethyl amide, diethylamide, N-methyl-propyl acid amides, N-isopropyl methyl acid amides, N-ethyl sec.-propyl acid amides, dipropyl acid amides, diisopropylamide, N-methyl butyl acid amides, N-ethyl-butyl acid amides, N-methyl-tert-butylamides, N-te t-butylisopropylamide, dibutyl acid amides, two-sec-butyl acid amides, diisobutyl acid amides, tert-pentyl-tert-butylamides, the diamyl acid amides, N-methyl hexyl acid amides, dihexyl acid amides, tert-pentyl-uncle's octyl group acid amides, dioctyl acid amides, two (2-ethylhexyl) acid amides, the didecyl acid amides, N-methyl octadecyl acid amides, N-methylcyclohexyl acid amides, N-ethyl cyclohexyl amide, N-isopropylcyclohexyl-acid amides, N-tert-butylcyclohexyl acid amides, dicyclohexyl acid amides, tetramethyleneimine, piperidines, hexamethylene imine, decahydroquinoline, pentanoic, N-methyl anilide (methylanilide) or N-ethyl anilide (ethylanilide).
L
1CAnd L
2CBe nitrogen or phosphorus separately independently of one another, nitrogen especially, and when v is 0 can with carry R
4COr R
5CCarbon atom form two keys.Especially, when v is 0, L
1CAnd/or L
2CWith carry R
4COr R
5CCarbon atom form imino--CR together
4C=N-or-CR
5C=N-.When v is 1, L
1CAnd/or L
2CWith carry R
4COr R
5CCarbon atom form together, especially, amide group-CR
4CR
6C-N--or-CR
5CR
7C-N
--.
Ligand X
CFor example derive from the selection of the synthetic suitable initial metallic compound that is used for iron complex, but also can be in change afterwards.Possible ligand X
CBe, especially, halogen such as fluorine, chlorine, bromine or iodine, especially chlorine.Alkyl such as methyl, ethyl, propyl group, butyl, vinyl, allyl group, phenyl or benzyl also are available ligand X
CAs other ligand X
C, purely for example and but enumerate exhaustively anything but, can mention the trifluoroacetic acid root, BF
4 -, PF
6 -With weak coordinate or non-coordinate negatively charged ion (referring to, S.Strauss in Chem.Rev.1993 for example, 93,927-942), B (C for example
6F
5)
4 -Acid amides, alkoxyl group, sulfonate radical, carboxylate radical and beta-diketon root also are useful especially ligand X
CAmong the ligand X of these replacements some are preferred especially uses, because they can obtain from starting raw material cheap and that be purchased easily.Therefore, particularly preferred example is X wherein
CBe dimethylformamide, methoxyl group, oxyethyl group, isopropoxy, phenoxy group, naphthyloxy, the trifluoromethanesulfonic acid root, right-tosylate, those of acetate moiety or methyl ethyl diketone acid group.
Radicals R
18CVariation for example make physicals such as solubleness to regulate subtly.Possible carbon organic substituent R
18CBe following groups for example: linearity or branching C
1-C
20-alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, (it can and then carry C to 5-to the first cycloalkyl of 7-
6-C
10-aryl is as substituting group), for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, C
2-C
20-alkenyl (it can be linear, and keys ring-type or branching and wherein two can be inner or terminal), vinyl for example, 1-allyl group, 2-allyl group, the 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, C
6-C
20-aryl (it can be replaced by other alkyl and/or the group that contains N-or contain O-), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2, the 6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl, 2-p-methoxy-phenyl, 2-N, N-dimethylamino phenyl, or arylalkyl (it can be replaced by alkyl), benzyl for example, adjacent-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein two radicals R
18CAlso can link to each other and form 5-or 6-unit ring and this organic radical R
18CAlso can be by halogen such as fluorine, chlorine or bromine replaces.At organosilicon substituting group SiR
19C 3In possible radicals R
19CBe for R with above
18CDescribed identical group, wherein two radicals R
19CAlso can link to each other and form 5-or 6-unit ring, for example trimethyl silyl, triethylsilyl, butyl dimetylsilyl, tributyl silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.The preferred C that uses
1-C
10-alkyl, as methyl, ethyl, n-propyl, normal-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and vinyl, allyl group, benzyl and phenyl are as radicals R
18C
Ligand X
CNumber s depend on the oxidation state of iron.Therefore this number s does not briefly provide.Normally those in this area are known to the skilled for the oxidation state of iron in the catalytic activity title complex.Yet, also might use such title complex, its oxidation state does not correspond to the oxidation state of active catalyst.This type of title complex can suitably reduce or oxidation by enough suitable activators then.Preferred use be in oxidation state+3 or+2 iron complex.
D is that no electric charge is given body, especially uncharged Lewis base or Lewis acid, amine for example, alcohols, ethers, ketone, aldehydes, the ester class, sulfide or phosphine class, it can be bonded in the iron center or still exist as the residual solvent in the preparation that derives from iron complex.
The number t of ligand D can be 0 to 4 and usually depend on the time that the solvent for preparing iron complex and gained title complex are dried and also can be that non-integer is as 0.5 or 1.5 therefore.Especially, t is 0,1 to 2.
Be in preferred embodiments
Wherein
E
2C-E
4CBe carbon separately independently of one another, nitrogen or phosphorus, carbon especially,
R
1C-R
3CBe hydrogen separately independently of one another, C
1-C
22-alkyl, C
2-C
22-alkenyl, C
6-C
22-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, halogen, NR in moieties
18C 2, OR
18C, SiR
19C 3, this organic radical R wherein
1C-R
3CAlso can be replaced and/or two ortho position radicals R by halogen
1C-R
3CAlso can link to each other form five-, six-or seven-membered ring, and/or two ortho position radicals R
1C-R
3CCombining to form to contain is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle,
R
4C-R
5CBe hydrogen separately independently of one another, C
1-C
22-alkyl, C
2-C
22-alkenyl, C
6-C
22-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, NR in moieties
18C 2, SiR
19C 3, this organic radical R wherein
4C-R
5CAlso can be replaced by halogen,
U is at E
2C-E
4CBe 0 and when being nitrogen or phosphorus at E
2C-E
4CBe 1 when being carbon,
L
1C-L
2CBe nitrogen or phosphorus separately independently of one another, nitrogen especially,
R
8C-R
11CBe C separately independently of one another
1-C
22-alkyl, C
2-C
22-alkenyl, C
6-C
22-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, halogen, NR in moieties
18C 2, OR
18C, SiR
19C 3, this organic radical R wherein
8C-R
11CAlso can be replaced and/or two ortho position radicals R by halogen
8C-R
17CAlso can link to each other form five-, six-or seven-membered ring, and/or two ortho position radicals R
8C-R
17CContinuous formation contains and is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle,
R
12C-R
17CBe hydrogen separately independently of one another, C
1-C
22-alkyl, C
2-C
22-alkenyl, C
6-C
22-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, halogen, NR in moieties
18C 2, OR
18C, SiR
19C3, this organic radical R wherein
12C-R
17CAlso can be replaced and/or two ortho position radicals R by halogen
8C-R
17CAlso can link to each other form five-, six-or seven-membered ring, and/or two ortho position radicals R
8C-R
17CContinuous formation contains and is selected from N, P, and five of at least one atom among O or the S-, six-or seven-first heterocycle,
Subscript v is 0 or 1 separately independently of one another,
Radicals X
CBe fluorine separately independently of one another, chlorine, bromine, iodine, hydrogen, C
1-C
10-alkyl, C
2-C
10-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, NR in moieties
18C 2, OR
18C, SR
18C, SO
3R
18C, OC (O) R
18C, CN, SCN, beta-diketon root, CO, BF
4 -, PF
6 -Or huge non-coordination anion and this radicals X
CCan be connected to each other,
Radicals R
18CBe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and has the alkylaryl of 6-20 carbon atom in aryl moiety, SiR in moieties
19C 3, this organic radical R wherein
18CAlso can be by halogen or nitrogenous-and replacement of oxygen containing group and two radicals R
18CAlso can link to each other forms five-or six-ring,
Radicals R
19CBe hydrogen separately independently of one another, C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl has 1-10 carbon atom and have the alkylaryl of 6-20 carbon atom in aryl moiety, wherein this organic radical R in moieties
19CAlso can be by halogen or nitrogenous-and replacement of oxygen containing group and two radicals R
19CAlso can link to each other forms five-or six-ring,
S is 1,2,3 or 4, especially 2 or 3,
D be no electric charge give body and
T is 0-4, especially 0,1 or 2.
Aforesaid example and preferred embodiment similarly are applicable to E
2C-E
4C, R
1C-R
3C, X
C, R
18CAnd R
19C
Substituent R
4C-R
5CCan in wide region, change.Possible carbon organic substituent R
4C-R
5CBe following groups for example: hydrogen, the C of linearity or branching
1-C
22-alkyl, methyl for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, (it can and then carry C to 5-to the first cycloalkyl of 7-
1-C
10-alkyl and/or C
6-C
10-aryl is as substituting group), cyclopropyl for example, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, C
2-C
22-alkenyl (it can be linear, and keys ring-type or branching and wherein two can be inner or terminal), vinyl for example, 1-allyl group, 2-allyl group, the 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, C
6-C
22-aryl (it can be replaced by other alkyl), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2, the 6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl, or arylalkyl (it can be replaced by other alkyl), benzyl for example, adjacent-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein this organic radical R
4C-R
5CAlso can be by halogen such as fluorine, chlorine or bromine replaces.In addition, R
4C-R
5CCan be amino N R
18C 2Or N (SiR
19C 3)
2, dimethylamino for example, N-pyrrolidyl or picolinyl.At organosilicon substituting group SiR
19C 3In possible radicals R
19CBe for R with above
1C-R
3CDescribed identical group, wherein two radicals R
19CAlso can link to each other forms 5-or 6-unit ring, trimethyl silyl for example, triethylsilyl, the butyl dimetylsilyl, tributyl silyl, tri-tert silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.These SiR
19C 3Group also can be keyed on the carbon that carries them via nitrogen.
Preferred radicals R
4C-R
5CBe hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or benzyl, especially methyl.
Substituent R
8C-R
17CCan in wide region, change.Possible carbon organic substituent R
8C-R
17CBe following groups for example: the C of linearity or branching
1-C
22-alkyl, methyl for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, (it can and then carry C to 5-to the first cycloalkyl of 7-
1-C
10-alkyl and/or C
6-C
10-aryl is as substituting group), cyclopropyl for example, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, C
2-C
22-alkenyl (it can be linear, and keys ring-type or branching and wherein two can be inner or terminal), vinyl for example, 1-allyl group, 2-allyl group, the 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, C
6-C
22-aryl (it can be replaced by other alkyl), phenyl for example, naphthyl, xenyl, anthryl, adjacent-,-, right-aminomethyl phenyl, 2,3-, 2,4-, 2,5-or 2, the 6-3,5-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4,5-trimethylphenyl, or arylalkyl (it can be replaced by other alkyl), benzyl for example, adjacent-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein two radicals R
8C-R
17CAlso can link to each other forms 5-, 6-or 7-unit ring and/or two ortho position radicals R
8C-R
17CCan link to each other to form to contain is selected from N, P, and five of at least one atom among O and the S-, six-or seven-first heterocycle and/or this organic radical R
8C-R
17CAlso can be by halogen such as fluorine, chlorine or bromine replaces.In addition, R
8C-R
17CCan be halogen such as fluorine, chlorine, bromine, amino N R
18C 2Or N (SiR
19C 3)
2, alkoxyl group or aryloxy OR
18C, dimethylamino for example, N-pyrrolidyl, picolinyl, methoxyl group, oxyethyl group or isopropoxy.At organosilicon substituting group SiR
19C 3In possible radicals R
19CBe for R with above
1C-R
3CMentioned identical carbon organic group, wherein two radicals R
19CAlso can link to each other forms 5-or 6-unit ring, trimethyl silyl for example, triethylsilyl, the butyl dimetylsilyl, tributyl silyl, tri-tert silyl, triallyl silyl, triphenyl silyl or 3,5-dimethylphenyl silyl.These SiR
19C 3Group also can come keyed jointing via oxygen or nitrogen, for example trimethyl silyl oxygen base, triethylsilyl oxygen base, butyl dimetylsilyl oxygen base, tributyl silyl oxygen base or tri-tert silyl oxygen base.
Preferred radicals R
12C-R
17CBe hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, fluorine, chlorine and bromine, especially hydrogen.Especially, R
13CAnd R
16CEach is methyl naturally, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, fluorine, chlorine or bromine and R
12C, R
14C, R
15CAnd R
17CEach is hydrogen naturally.
Preferred radicals R
8C-R
11CBe methyl, trifluoromethyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl group, benzyl, phenyl, fluorine, chlorine and bromine.Especially, R
8CAnd R
10CEach is C naturally
1-C
22-alkyl (it also can be replaced by halogen), especially C
1-C
22-positive alkyl (it also can be replaced by halogen), methyl for example, trifluoromethyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, or halogen such as fluorine, chlorine or bromine and R
9CAnd R
11CEach is halogen such as fluorine naturally, chlorine or bromine.Particularly preferably be R
8CAnd R
10CRespectively be C
1-C
22-alkyl (it also can be replaced by halogen), especially C
1-C
22-positive alkyl (it also can be replaced by halogen), methyl for example, trifluoromethyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl and R
9CAnd R
11CEach is halogen such as fluorine naturally, chlorine or bromine.
Especially, R
12C, R
14C, R
15CAnd R
17CBe identical, R
13CAnd R
16CBe identical, R
9CAnd R
11CBe identical and R
8CAnd R
10CBe identical.This also is preferred in aforesaid preferred embodiment.
Compd B) preparation is described in for example J.Am.Chem.Soc.120, p.4049 reaches thereafter (1998), J.Chem.Soc., Chem.Commun.1998,849 and WO 98/27124 in.Preferred complexes B) is dichloro 2,6-is two, and [1-(2,6-3,5-dimethylphenyl imino-) ethyl] pyridine closes iron (II), dichloro 2,6-is two, and [1-(2,4,6-trimethylphenyl imino-) ethyl] pyridine closes iron (II), dichloro 2, two [1-(the 2-chloro-6-aminomethyl phenyl imino-) ethyl] pyridines of 6-close iron (II), dichloro 2, two [1-(2, the 6-diisopropyl phenyl imino-) ethyl] pyridines of 6-close iron (II), dichloro 2,6-is two, and [1-(2,6-dichlorophenyl imino-) ethyl] pyridine closes iron (II), dichloro 2,6-is two, and [1-(2,6-diisopropyl phenyl imino-) methyl] pyridine closes iron (II), dichloro 2, two [1-(2, the 4-two chloro-6-aminomethyl phenyl imino-s) ethyl] pyridines of 6-close iron (II), dichloro 2, two [1-(2, the 6-difluorophenyl imino-) ethyl] pyridines of 6-close iron (II), dichloro 2, two [1-(2, the 6-dibromo phenyl imino-) ethyl] pyridines of 6-close iron (II) or corresponding dibromide or tribromo-compound.
Hereinafter, mean monocyclopentadienyl title complex (A1) and/or luxuriant hafnium (A2) about transition metal complex (A) or catalyzer (A).Transition metal complex A) with polymerizing catalyst B) molar ratio normally 1: 100-100: 1, in preferred 1: 10 to 10: 1 and preferred 1: 5 to 5: the 1 especially scope.As transition metal complexes A) in the homopolymerization of ethene or copolymerization under identical reaction conditions during as unique catalyzer, it preferably produces higher Mw, and the Mw that is reached with this title complex (B) when title complex (B) is used as unique title complex under identical reaction conditions compares.Title complex (A1), preferred embodiment (A2) and (B) is preferred in title complex (A1) and combination (B) and in title complex (A2) and combination (B) equally.
Catalyst composition of the present invention can be separately or with the catalyst system of other component as olefinic polyreaction.In addition, we find that the catalyst system of olefinic polyreaction comprises
A) based on the monocyclopentadienyl title complex (A1) of the metal of the 4-6 family of the periodic table of elements or at least a polymerizing catalyst of luxuriant hafnium (A2), the cyclopentadienyl system of described monocyclopentadienyl title complex is not had electric charge and is replaced to body,
B) carry at least two neighbours to have, the iron component of the tridentate ligand of neighbour-dibasic aryl is at least a polymerizing catalyst on basis,
C) choose any one kind of them or multiple activation compound,
D) Ren Xuan one or more organic or inorganic carriers,
E) one or more metallic compounds of the metal of the Ren Xuan periodic table of elements 1,2 or 13 families.
Hereinafter, mean monocyclopentadienyl title complex (A1) and/or luxuriant hafnium (A2) about transition metal complex (A) or catalyzer (A).Transition metal complex A) with polymerizing catalyst B) molar ratio normally 1: 100-100: 1, in preferred 1: 10 to 10: 1 and preferred 1: 5 to 5: the 1 especially scope.As transition metal complexes A) in the homopolymerization of ethene or copolymerization under identical reaction conditions during as unique catalyzer, it preferably produces higher Mw, and the Mw that is reached with this title complex (B) when title complex (B) is used as unique title complex under identical reaction conditions compares.Title complex (A1), preferred embodiment (A2) and (B) is preferred in title complex (A1) and combination (B) and in title complex (A2) and combination (B) equally.
This monocyclopentadienyl title complex (A1), luxuriant hafnium (A2) and/or iron complex (B) only have low polymerization activity sometimes and need with one or more activators then is that component (C) contacts, in order that can demonstrate good polymerization activity.Therefore catalyst system comprises further randomly that as component (C), one or more activate uses compounds, preferably one or both activation compounds (C).Catalyst system of the present invention preferably includes one or more activators (C).Depend on this catalyst combination (A) and (B), one or more activation are favourable with compound (C).The transition metal complex of catalyst composition (A) can be undertaken by using identical activator or activating mixtures or different activators with activation iron complex (B).Usually it is desirable to use identical activator (C) for both for catalyzer (A) and (B).
Activator (C) can be according to using based on the title complex (A) of catalyst composition of the present invention and any amount (B) under each situation.They are preferably with excessive or use by stoichiometry, under each situation based on their institute's activatory title complexs (A) or (B).The type of this activator (C) is depended in activation with the consumption of compound.Usually, transition metal complex (A) can be 1: 0.1 to 1: 10000 with the molar ratio that activates with compound (C), preferred 1: 1 to 1: 2000.Iron complex (B) and activation use the molar ratio of compound (C) also normally 1: 0.1-1: 10000, preferred 1: 1-1: in 2000 scopes.
The suitable combination thing (C) that can make it to change into catalytic activity or more active compounds with the reaction of transition metal complex (A) or iron complex (B) for example is such as aikyiaiurnirsoxan beta, strong no electric charge Lewis acid has the cationic ionic compound of Lewis acid or contains the compound of Bronsted acid as cationic ionic compound and so on.
As aikyiaiurnirsoxan beta, might use, for example, be described in the compound among the WO 00/31090.Useful especially aikyiaiurnirsoxan beta is general formula (X) or open chain (XI) or ring-type aluminium alkoxide compound
R wherein
1D-R
4DBe C separately independently of one another
1-C
6-alkyl, preferable methyl, ethyl, butyl or isobutyl-and l are 1 to 40, preferred 4 to 25 integer.
Useful especially aluminium alkoxide compound is a methylaluminoxane.
These the oligomeric aluminium alkoxide compounds normally controlled reaction of the solution by trialkylaluminium (especially trimethyl aluminium) and water prepare.Usually, the oligomeric aluminium alkoxide compound that is obtained is the form of the mixture of the linearity of all lengths and closed chain molecule, and therefore 1 is considered to mean value.This aluminium alkoxide compound also can exist with mixture with other metal alkylide (being generally aluminum alkyls).The aikyiaiurnirsoxan beta preparation that is suitable as component (C) can have been bought from the market.
In addition, the alkyl that also can use some of them is by hydrogen atom or alkoxyl group, and aryloxy, siloxy-or amide group alternate modified alumoxane replace general formula (X) or aluminium alkoxide compound (XI) as component (C).
Have been found that and it is desirable to use transition metal complex A) or iron complex B) and aluminium alkoxide compound, its consumption makes that be 1 from the aluminium in the aluminium alkoxide compound that comprises any aluminum alkyls that still exists with atomic ratio from the transition metal in the transition metal complex (A): 1-2000: 1, preferred 10: 1-500: 1 and especially 20: 1-400: in 1 the scope.From the aluminium in the aluminium alkoxide compound that comprises still any aluminum alkyls that exists with from the atomic ratio of the iron in the iron complex (B) normally 1: 1-2000: 1, preferred 10: 1-500: 1 and especially 20: 1-400: in 1 the scope.
The suitable activation of other type is a hydroxyai upsilonminoxanes with component (C).These can, for example, by add the normal water of every normal aluminium 0.5-1.2 in alkylaluminium cpd (especially triisobutyl aluminium) under low temperature (being usually less than 0 ℃), the preferred normal water of 0.8-1.2 prepares.This compounds and their uses in olefinic polyreaction for example are described among the WO 00/24787.From the aluminium in the hydroxyai upsilonminoxanes compound with from the atomic ratio of the transition metal in transition metal complex (A) or the iron complex (B) normally 1: 1-100: 1, preferred 10: 1-50: 1 and especially 20: 1-40: in 1 the scope.Preferred monocyclopentadienyl metal dialkyl compound (A1) or the luxuriant hafnium dialkyl compound (A2) used.
As strong no electric charge Lewis acid, the preferably compound of general formula (XII)
M
2DX
1DX
2DX
3D (XII)
Wherein
M
2DBe the element of the periodic table of elements 13 families, B especially, Al or Ga, preferred B,
X
1D, X
2DAnd X
3DEach is hydrogen naturally, C
1-C
10-alkyl, C
6-C
15-aryl, alkylaryl, arylalkyl, haloalkyl or halogen aryl have 1-10 carbon atom and have 6-20 carbon atom in aryl moieties in each comfortable moieties, or fluorine, chlorine, bromine or iodine, especially halogen aryl, preferably pentafluorophenyl group.
Lewis acidic other example of strong no electric charge provides in WO 00/31090.
The compound that can be used as component (C) especially is borine and boroxin such as trialkylborane, triarylborane or trimethylboroxin.The preferred especially borine that carries at least two perfluorination aryl that uses.Particularly preferably be the compound of general formula (XII), wherein X
1D, X
2DAnd X
3DBe identical, triphenylborane for example, three (4-fluorophenyl) borine, three (3, the 5-difluorophenyl) borine, three (4-methyl fluoride phenyl) borine, three (pentafluorophenyl group) borine, three (tolyl) borine, three (3, the 5-3,5-dimethylphenyl) borine, three (3, the 5-difluorophenyl) borine or three (3,4, the 5-trifluorophenyl) borine.Preferred three (pentafluorophenyl group) borine that uses.
Suitable compound (C) is preferably passed through aluminium or the boron compound and the water of general formula (XII), alcohol, and phenol derivatives, the reaction of thiophenol derivative or anils prepares, and wherein halo and especially fluoridized alcohols and phenols are particularly importants.The example of useful especially compound is a Pentafluorophenol, 1, and two (pentafluorophenyl group) methyl alcohol of 1-and 4-hydroxyl-2,2 ', 3,3 ', 4 ', 5,5 ', 6,6 '-nine fluorine biphenyl.The example of the combination of the compound of general formula (XII) and cloth youth Si Tede acid is, especially, and trimethyl aluminium/Pentafluorophenol, two (pentafluorophenyl group) methyl alcohol of trimethyl aluminium/1-, trimethyl aluminium/4-hydroxyl-2,2 ', 3,3 ', 4 ', 5,5 ', 6,6 '-nine fluorine biphenyl, triethyl aluminum/Pentafluorophenol and triisobutyl aluminium/Pentafluorophenol and triethyl aluminum/4,4 '-dihydroxyl-2,2 ', 3,3 ', 5,5 ', 6,6 '-octafluoro biphenyl hydrate.
In other suitable aluminium and boron compound of general formula (XII), R
1DBe the OH group, for example in a borinic acid (boronic acid) and borinic acid (borinic acid).Can mention the borinic acid with perfluorination aryl, for example (C especially
6F
5)
2BOH.
Be suitable as activation and comprise also that with the strong no electric charge Lewis acid of compound (C) reaction product of the reaction between a borinic acid and two the normal trialkylaluminiums or trialkylaluminium and two normal acidity fluoridizes the reaction product of the reaction between (especially perfluorination) carbon compound such as Pentafluorophenol or two (pentafluorophenyl group) borinic acid.
Have the cationic appropriate ions compound of Lewis acid and comprise the cationic salt shape compound of general formula (XIII)
[((M
3D)
a+)Q
1Q
2...Q
z]
d+ (XIII)
Wherein
M
3DBe the element of the 1-16 family of the periodic table of elements,
Q
1-Q
zOnly be electronegative group such as C
1-C
28-alkyl, C
6-C
15-aryl, alkylaryl, arylalkyl, haloalkyl, the halogen aryl has 6-20 carbon atom and have 1-28 carbon atom, C in moieties in each comfortable aryl moiety
3-C
10(it can carry C to cycloalkyl
1-C
10Alkyl is as substituting group), halogen, C
1-C
28-alkoxyl group, C
6-C
15-aryloxy, silyl or sulfydryl,
A be 1 to 6 integer and
Z is 0 to 5 integer,
D is equivalent to difference a-z, but d is more than or equal to 1.
Useful especially positively charged ion is a carbocation, oxygen positively charged ion and sulfonium cation and cationic transition metal title complex.Can mention the trityl positively charged ion especially, silver-colored positively charged ion and 1,1 '-dimethyl ferrocenyl positively charged ion.They preferably have non-coordination counter ion, the boron compound of especially also mentioning in WO91/09882, preferred four (pentafluorophenyl group) borate.
Salt with non-coordination anion also can be by (it can react and be connected two or more boron or aluminium atom with second kind of compound with boron or aluminum compound (for example aluminum alkyls), water for example), (it and boron or aluminum compound form the ionization ionic compound with the third compound, triphenylmethyl chloride for example), or optional alkali, the alkali of preferred organic nitrogen-containing, amine for example, anils or nitrogen heterocyclic blending prepare.In addition, can add similarly the 4th kind of compound, for example Pentafluorophenol with boron or aluminum compound reaction.
Contain Bronsted acid and preferably similarly have non-coordination counter ion as cationic ionic compound.As Bronsted acid, particularly preferably be protonated amine or anils.Preferred cation is N, N-dimethyl puratized agricultural spray, N, N-Dimethylcyclohexyl ammonium and N, N-dimethyl benzyl ammonium and both derivatives of back.
The negatively charged ion boron heterocyclic compound that contains that is described among the WO 9736937 also is suitable as component (C), especially assorted benzene (boratabenzene) of dimethyl puratized agricultural spray boron or the assorted benzene of trityl boron.
Preferred ionic compound C) contains the borate that carries at least two perfluorination aryl.Particularly preferably be N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borates and N especially, N-Dimethylcyclohexyl ammonium four (pentafluorophenyl group) borate, N, N-dimethyl benzyl ammonium four (pentafluorophenyl group) borate or trityl four (pentafluorophenyl group) borate.
Two or more borate anion also might be connected to each other, as with dianion [(C
6F
5)
2B-C
6F
4-B (C
6F
5)
2]
2-Form, or borate anion can be bonded in appropriate functional group on carrier surface via abutment.
Other suitable activation is listed in WO 00/31090 with compound (C).
Strong no electric charge Lewis acid, have the cationic ionic compound of Lewis acid or contain Bronsted acid as the consumption of cationic ionic compound 0.1-20 equivalent preferably, more preferably 1-10 equivalent and especially preferably 1-2 equivalent are based on transition metal complex (A) or iron complex (B).
Suitable activation also comprises boron-aluminum compound with compound (C), as two [two (pentafluorophenyl group boron oxygen base)] aluminium trimethide alkane.The example of this type of boron-aluminum compound is to be disclosed among the WO 99/06414 those.
Also might use the mixture of all above-mentioned activation with compound (C).Preferred mixture comprises aikyiaiurnirsoxan beta, and especially methylaluminoxane, and ionic compound especially contains the compound of four (pentafluorophenyl group) borate anion and/or strong no electric charge Lewis acid, especially three (pentafluorophenyl group) borine or boroxins.
Transition metal complex (A) or iron complex (B) and activation are preferably used in solvent with compound (C), and the latter preferably has the aromatic hydrocarbon of 6-20 carbon atom, especially dimethylbenzene, toluene, pentane, hexane, heptane or their mixture.
Also might use the activation compound (C) that can be used as carrier (D) simultaneously.This type of system for example can be from handling inorganic oxide and obtaining with post chlorization (for example using tetracol phenixin) with zirconium alkoxide.The preparation of this type of system for example is described among the WO 01/41920.
(C) preferred embodiment with (A) and/or the combination of preferred embodiment (B) be particularly preferred.
As catalyst component (A) and associating activator (C) (B), preferably use aikyiaiurnirsoxan beta.Also preferably, activator (C) as luxuriant hafnium (A2), the cationic salt shape compound of general formula (XIII) (N especially, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate, N, N-Dimethylcyclohexyl ammonium four (pentafluorophenyl group) borate, N, N-dimethyl benzyl ammonium four (pentafluorophenyl group) borate or trityl four (pentafluorophenyl group) borate) combination, especially with the combined form of aikyiaiurnirsoxan beta as the activator (C) of iron complex (B).
Other useful especially associating activator (C) is the reaction product of aluminum compound and the perfluorination alcohols and the phenols of general formula (XII).
In order to make this transition metal complex (A) and this iron complex (B) be used for the polymerization process of gas phase or suspension, usually advantageously use the title complex of solid form, promptly they can put on the solid carrier (D).In addition, the title complex that supports has high productivity.Therefore this transition metal complex (A) and/or this iron complex (B) can also randomly be fixed on organic or inorganic carrier (D) and upward and with the form that supports be used for polyreaction.This makes that for example, the deposition in reactor can be avoided can controlling with polymer morphology.As solid support material, preferred silica gel, magnesium chloride, the aluminum oxide of using, mesopore material, aluminosilicate, hydrotalcite and organic polymer such as polyethylene, polypropylene, polystyrene, tetrafluoroethylene or carry the polymkeric substance of polar functional group, for example ethene and esters of acrylic acid, the multipolymer of propenal or vinyl-acetic ester.
Particularly preferably be and comprise at least a transition metal complex (A), at least a iron complex (B), at least a activation catalyst system of compound (C) and at least a carrier component (D).
Preferred catalyst compositions according to the present invention comprises one or more carrier component.Both might be supported this transition metal component (A) and iron complex (B), or only a kind of can the supporting in two kinds of components.In preferred embodiments, this component (A) and (B) both support.Two kinds of components (A) can be applied on the different carriers in this case with (B) or put on together on the carrier of associating.This component (A) and (B) preferably being applied on the carrier of associating, so as the close relatively space of guaranteeing various catalyst center near and so guarantee the well blend of formed different polymkeric substance.
In order to prepare catalyst system of the present invention, preferably by physical adsorption or to rely on chemical reaction be the covalency keyed jointing of component, a kind of component (A) and a kind of component (B) and/or activator (C) or carrier (D) are fixed with the reaction active groups on the carrier surface.
Carrier component D wherein), transition metal complex (A), iron complex (B) and this activation are unessential with the mixed order of compound (C) in principle.After each processing step, various intermediates can enough suitable inert solvents such as aliphatics or aromatic hydrocarbon washing.
Transition metal complex (A), iron complex (B) and this activation can be fixed independently of one another with compound (C), for example succeedingly or side by side.Therefore, this carrier component (D) can be at first contact with compound (C) with activation or this carrier component (D) can at first contact with transition metal complex (A) and/or iron complex (B).With before carrier (D) mixes, transition metal complex A) utilizing one or more activation also is possible with pre-activation of compound (C).This iron component can, for example, simultaneously with transition metal complex and with activating compounds (C) reaction, maybe can utilize the latter to come to activate in advance independently.Preactivated iron complex (B) can be applied on the carrier before or after preactivated transition metal complex (A).In a possible embodiment, transition metal complex (A) and/or iron complex (B) also can prepare in the presence of solid support material.Other method of fixed is to be with or without the prepolymerization of carrying out catalyst system under the condition that puts in advance on the carrier.
Should fixing generally carry out in inert solvent, this solvent can be removed by filtering or evaporating after fixing.After each processing step, solid can be with inert solvent such as aliphatics or the aromatic hydrocarbon washing that suits with dry then.Yet still Shi catalyst-loaded use also is possible.
In the preferred method of the preparation of catalyst-loaded system, at least a iron complex (B) contacts with activatory compound (C) and mixes with the solid support material (D) of dehydration or passivation subsequently.Transition metal complex (A) similarly contacts in suitable solvent with compound (C) with at least a activation, preferably obtains the reaction product of solubility, adduct or mixts.In this way the preparation product of Huo Deing mixes with fixed iron complex (it can directly or after separating solvent use) then, and solvent is completely or partially removed then.The catalyst-loaded system preference drying of gained is removed from the hole of solid support material to guarantee whole or most solvent.Catalyst-loadedly preferably obtain as the easy mobility powder.The embodiment of the industrial implementation scheme of above method is described in WO 96/00243, among WO 98/40419 or the WO 00/05277.Other preferred embodiment comprise at first produce the activation that is supported on the carrier component (D) with compound (C) with this compound that supports contacts with iron complex (B) with transition metal complex (A) with relief.
As carrier component (D), preferably use finely divided carrier, the latter can be any organic or inorganic solid.Especially, this carrier component (D) can be porous support such as talcum, and sheet silicate if you would take off soil, mica or inorganic oxide or finely divided polymer powder (for example polyolefine or have the polymkeric substance of polar functional group).
Employed solid support material preferably has 10-1000m
2The specific surface area of/g, the mean particle size of the void content of 0.1-5ml/g and 1-500 μ m.Preferably specific surface area is at 50-700m
2In/g the scope, void content is the carrier in the 5-350 mu m range at 0.4-3.5ml/g and mean particle size.Particularly preferably be specific surface area at 200-550m
2In/g the scope, void content is the carrier in the 10-150 mu m range at 0.5-3.0ml/g and mean particle size.
This transition metal complex (A) preferably uses with a kind of like this consumption, make that the content of transition metal of transition metal complex in the finished catalyst system (A) is 1-200 μ mol, preferred 5-100 μ mol and preferred especially 10-70 μ mol, the carrier of every g (D).This iron complex (B) preferably uses with a kind of like this consumption, makes that the content of iron of iron complex in the finished catalyst system (B) is 1-200 μ mol, preferred 5-100 μ mol and especially preferred 10-70 μ mol, the carrier of every g (D).
This inorganic carrier can be heat-treated, and for example removes adsorbed water.This drying treatment generally is to carry out under 50-1000 ℃, preferred 100-600 ℃ temperature, wherein preferably under reduced pressure and/or in the atmosphere of rare gas element (for example nitrogen) carry out, or inorganic carrier can be at 200-1000 ℃ temperature lower calcination with the solid of producing desired structure and/or be adjusted in lip-deep required OH content in the drying under 100-200 ℃.This carrier also can be by using common siccative such as metal alkylide, preferred alkyl aluminium, chlorosilane or SiCl
4, or methylaluminoxane is handled with chemical mode.Suitable treatment process for example is described among the WO 00/31090.
Inorganic carrier material also can the chemical mode modification.For example, silica gel NH
4SiF
6Or the processing of other fluorizating agent can cause fluoridizing of silica gel surface, or silica gel is nitrogenous with containing, the processing of the silane of the group of fluorine or sulphur can obtain the silica gel surface of corresponding modification.
Organic support material such as finely divided polyolefin powder (for example polyethylene, polypropylene or polystyrene) also can use and preferably similarly be removed appended moisture, solvent residues or other impurity by suitable purification and drying operation before using.Also might use the functionalized polymeric carrier, for example with polystyrene, polyethylene, polypropylene or polybutene are basic person, utilize its functional group's (for example ammonium or hydroxyl) that at least a catalyst component is fixed.Also might use blend polymer.
The inorganic oxide that is suitable as carrier component (D) can find in the oxide compound of the element of 2,3,4,5,13,14,15 and 16 families of the periodic table of elements.Preferably the example as the oxide compound of carrier comprises silicon-dioxide, aluminum oxide and element calcium, aluminium, silicon, the mixed oxide of magnesium or titanium and corresponding oxide mixture.Can use separately or with other inorganic oxide of the combined use of above-mentioned preferred oxide carrier for example be MgO, CaO, AlPO
4, ZrO
2, TiO
2, B
2O
3Or their mixture.
Other preferred inorganic carrier material is inorganic halides such as MgCl
2Or carbonate such as Na
2CO
3, K
2CO
3, CaCO
3, MgCO
3, vitriol such as Na
2SO
4, Al
2(SO
4)
3, BaSO
4, nitrate such as KNO
3, Mg (NO
3)
2Or Al (NO
3)
3
Solid carrier material (D) as the catalyzer of olefinic polyreaction preferably uses silica gel because granularity that they had and structure make that they are suitable as those particles of the carrier of olefinic polyreaction can be from this material produce.Spray-dired silica gel, it is the relatively little spherical agglomerated thing of particulate, promptly primary granule has been considered to useful especially.Silica gel can drying and/or calcination before using.
Other preferred carrier (D) is hydrotalcite and calcination hydrotalcite.In mineralogy, hydrotalcite is the natural mineral with following desired form
Mg
6Al
2(OH)
16CO
3·4H
2O
Its structure is from brucite Mg (OH)
2Structure derive from.Brucite is to carry out crystallization with sheet structure, wherein in the octahedra hole between two-layer close-packed hydroxyl ion metal ion is arranged, but only every second layer in octahedra hole is occupied.In hydrotalcite, some magnesium ions are substituted by aluminum ion, and the result is that the bag (packet) of these layers obtains positive charge.This comes balance by the negatively charged ion that is arranged in the intermediary layer with crystal water.
This type of sheet structure not only can be in magnesium-aluminium-oxyhydroxide, and generally can find in the mixed metal hydroxides of following general formula:
M(II)
2x 2+M(III)
2 3+(OH)
4x+4·A
2/n n-·zH
2O
It has sheet structure and wherein M (II) be divalent metal such as Mg, Zn, Cu, Ni, Co, Mn, Ca and/or Fe and M (III) are trivalent metal such as Al, Fe, Co, Mn, La, Ce and/or Cr, x is 0.5 to 10 number (is one-level with 0.5), and A is that gap negatively charged ion and n are the electric charges (it can be 1 to 8, common 1 to 4) on the negatively charged ion of gap, with z be 1 to 6,2 to 4 integer especially.Possible gap negatively charged ion is organic anion such as alkoxyl group negatively charged ion, and alkyl oxide sulfate radical, aryl ethers sulfate radical or glycol ether sulfate radical, inorganic anion be carbonate especially for example, bicarbonate radical, nitrate radical, chlorine root, sulfate radical or B (OH)
4 -Or polyoxy anionic metal (polyoxometal anion) is as Mo
7O
24 6-Or V
10O
28 6-Yet multiple this type of anionic mixture also is possible.
Therefore, whole these type of mixed metal hydroxides with sheet structure should be considered to be suitable for hydrotalcite of the present invention.
The calcination hydrotalcite can from the hydrotalcite preparation, whereby, especially, can be regulated required hydroxide radical group content by calcining (i.e. heating).In addition, this crystalline structure also changes.The preparation of calcination hydrotalcite used according to the invention is normally carried out being higher than under 180 ℃ the temperature.Preferably at 250 ℃ to 1000 ℃, the especially calcining of 3-24 hour time under 400 ℃-700 ℃ the temperature.Might allow air or rare gas element on solid by or apply vacuum simultaneously.
When heating, natural or synthetic hydrotalcite is at first sloughed water, promptly carries out drying.In further heating, during promptly actual the calcining, metal hydroxides changes into metal oxide by the anionic cancellation of hydroxyl and gap; OH group or gap negatively charged ion such as carbonate also can still be present in this calcination hydrotalcite.Its tolerance is the loss when calcination.This is the weight loss that sample experienced that heats in two steps, at first in drying oven 200 ℃ following 30 minutes and following 1 hour at 950 ℃ in retort furnace then.
As the calcination hydrotalcite of component (D) is the mixed oxide of divalence and trivalent metal M (II) and M (III) therefore, and wherein M (II) generally is at 0.5-10 with the molar ratio of M (III), preferably 0.75-8 and especially in the scope of 1-4.In addition, the impurity of normal amount, Si for example, Fe, Na, Ca or Ti and chlorine root and sulfate radical also can exist.
Preferred calcination hydrotalcite (D) is a mixed oxide, and wherein M (II) is that magnesium and M (III) are aluminium.This eka-aluminum-magnesium mixed oxide can be from Condea Chemie GmbH (SasolChemie now), and Hamburg obtains with trade(brand)name Puralox Mg.
Also calcination hydrotalcite preferably, wherein structural transformation is completely or virtually completely.Calcining, i.e. the conversion of structure can for example confirm with X-ray diffractogram.
Employed hydrotalcite, calcination hydrotalcite or silica gel are general as having 5-200 μ m, preferred 10-150 μ m, preferred especially 15-100 μ m and especially the finely divided powder of the median size D50 of 20-70 μ m use, and have 0.1-10cm usually
3/ g, preferred 0.2-5cm
3The volume of voids of/g, and 30-1000m
2/ g, preferred 50-800m
2/ g and 100-600m especially
2The specific surface area of/g.This transition metal complex (A) is preferably used with a kind of like this amount, make that the content of transition metal of transition metal complex in the finished catalyst system (A) is 1-100 μ mol, preferred 5-80 μ mol and preferred especially 10-60 μ mol, the carrier of every g (D).
Catalyst system may further include, as annexing ingredient (E), and the metallic compound of general formula (XX),
M
G(R
1G)
rG(R
2G)
sG(R
3G)
tG (XX)
Wherein
M
GBe Li, Na, K, Be, Mg, Ca, Sr, Ba, boron, aluminium, gallium, indium, thallium, zinc, Li especially, Na, K, Mg, boron, aluminium or Zn,
R
1GBe hydrogen, C
1-C
10-alkyl, C
6-C
15-aryl, alkylaryl or arylalkyl have 1-10 carbon atom and have 6-20 carbon atom in aryl moieties in each comfortable moieties,
R
2GAnd R
3GEach is hydrogen naturally, halogen, C
1-C
10-alkyl, C
6-C
15-aryl, alkylaryl, arylalkyl or alkoxyl group have 1-20 carbon atom and have 6-20 carbon atom in aryl moieties in each comfortable moieties, or and C
1-C
10-alkyl or C
6-C
15-aryl alkoxyl group together,
r
GIt is 1 to 3 integer
With
s
GAnd t
GBe 0 to 2 integer, summation r wherein
G+ s
G+ t
GBe equivalent to M
GValence state,
Wherein this component (E) is to be different from component (C) usually.Also might use the mixture of the various metallic compounds of general formula (XX).
Among the metallic compound of general formula (XX), preferably such compounds, wherein
M
GBe lithium, magnesium, boron or aluminium and
R
1GBe C
1-C
20-alkyl.
The particularly preferred metallic compound of general formula (XX) is a lithium methide, lithium ethide, n-Butyl Lithium, methylmagnesium-chloride, methyl-magnesium-bromide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride, dimethyl magnesium, magnesium ethide, dibutylmagnesium, normal-butyl-n-octyl magnesium, normal-butyl-n-heptylmagnesium, especially normal-butyl-n-octyl magnesium, three-n-hexyl aluminium, triisobutyl aluminium, three-n-butylaluminum, triethyl aluminum, dimethylaluminum chloride, dimethylaluminum fluoride, methylaluminum dichloride, methylaluminum sesquichloride, diethyl aluminum chloride and trimethyl aluminium and their mixture.The partial hydrolysate of aluminum alkyls and alcohols also can use.
When using metallic compound (E), it preferably is present in the catalyst system with such amount, and this amount makes the M of general formula (XX)
GWith the molar ratio from the summation of the transition metal of transition metal complex (A) and iron complex (B) be 3000: 1-0.1: 1, preferred 800: 1-0.2: 1 and preferred especially 100: 1-1: 1.
Usually, the metallic compound (E) of general formula (XX) is as the composition of the catalyst system of the polyreaction of alkene or copolymerization.Here, metallic compound (E) can for example be used for preparing the catalyst solid that comprises carrier (D) and/or add soon during the polyreaction or before polyreaction.Employed metallic compound (E) can be identical or different.Especially when this catalyst solid does not contain activation with component (C), catalyst system also might further comprise, except that this catalyst solid, the activation compound (C) that one or more any compound (E) with existing in catalyst solid is identical or different.
This component E) can (B) react similarly according to any order and component (A) with optional (C) with (D).This component (A) can be for example with contact with component (C) and/or (D) before or after want polymeric alkene contacts.With olefin before by one or more components (C) pre-activation and also be possible at this mixture with identical or another kind of component (C) after alkene contacts and/or further interpolation (D).Activate in advance generally at 10-100 ℃, carry out under preferred 20-80 ℃ the temperature.
In a further preferred embodiment, catalyst solid is from aforesaid component (A), (B), (C) with (D) preparation and it in the process of polyreaction, the beginning or before polyreaction, contact with component (E) soon.
Preferably at first allow component (E) contact and add subsequently comprise aforesaid component (A) with the alpha-olefin of want polymkeric substance, (B), (C) and catalyst solid (D).
In a further preferred embodiment, this carrier (D) at first contacts with component (E), and component (A) and (B) and any other activator (C) then by handling as mentioned above.
Also might allow catalyst system at first with alpha-olefin, preferred linear C
2-C
10-1-alkene and especially ethene or propylene carry out prepolymerization, the pre-polymerized catalyst solid of gained is used for actual polyreaction then.Catalyst solid that uses in prepolymerization and the polymerization monomeric quality ratio on it is normally 1: 0.1-1: 1000, preferred 1: 1-1: in 200 scopes.
In addition, a spot of alkene, preferred alpha-olefin, vinyl cyclohexane for example, vinylbenzene or phenyl dimethyl vinyl silanes, as modified component, antistatic or suitable inert compound such as wax or oil can be in the preparation process of catalyst system or are added as additive afterwards.The molar ratio of the summation of additive and transistion metal compound (A) and iron complex (B) normally 1: 1000 to 1000: 1, preferred 1: 5 to 20: 1.
Catalyst composition of the present invention or catalyst system are suitable for preparing polyethylene of the present invention, and the latter has ideal and uses and processing characteristics.
In order to prepare polyethylene of the present invention, make ethene carry out polymerization by method as mentioned above and alpha-olefin with 3-12 carbon atom.
In process for copolymerization of the present invention, ethene carries out polymerization with the alpha-olefin with 3-12 carbon atom.Preferred alpha-olefin is linearity or branching C
2-C
12-1-alkene, especially linear C
2-C
10-1-alkene, as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene or branching C
2-C
10-1-alkene such as 4-methyl-1-pentene.Particularly preferred alpha-olefin is C
4-C
12-1-alkene, especially linear C
6-C
10-1-alkene.Mixture that also might the various alpha-olefins of polymerization.Preferably polymerization is selected from ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, at least a alpha-olefin in 1-octene and the 1-decene.Containing at least, the monomer mixture of the ethene of 50mol% is preferred the use.
The inventive method of ethene and alpha-olefine polymerizing can be by using all industrial known polymerisation process, at-60-350 ℃, under the interior temperature of preferred 0-200 ℃ and preferred especially 25-150 ℃ of scope, with at 0.5-4000 crust, carry out under the pressure of preferred 1-100 crust and preferred especially 3-40 crust.Polyreaction can be in the known manner in body, and in suspension, the common reactor in the polyreaction that is used for alkene in gas phase or in supercritical medium carries out.It can or preferably carry out continuously on one or more grades of discontinuous ground.High pressure polymerization process in tubular reactor or autoclave, solution methods, suspension method, microgas phase method and phase fluidised bed processes all are possible.
Polyreaction is preferably carried out under the temperature in 20-300 ℃ of scope and under the pressure of 0.5-4000 crust normally in-60-350 ℃ scope.Mean residence time normally 0.5 to 5 hour, preferred 0.5 to 3 hour.The ideal pressure and temperature scope of carrying out polyreaction depends on polymerization process usually.For high pressure polymerization process, it especially carries out under the pressure of 2000-3500 crust normally at the 1000-4000 crust, and high polymerization temperature is generally also set.The ideal temperature scope of these high pressure polymerization process is 200-320 ℃, especially 220-290 ℃.For the low-pressure polymerization method, set usually than the polymkeric substance softening temperature temperature in low at least several years.Especially, in these polymerization processs, set 50-180 ℃, preferred 70-120 ℃ temperature.For suspension polymerization, polyreaction is usually in suspension medium (mixture of preferred unreactive hydrocarbons such as Trimethylmethane or hydrocarbon) or carry out in monomer itself.Polymeric reaction temperature generally is in-20-115 ℃ scope and this pressure generally is in 1-100 crust scope.The solids content of suspension generally is in the 10-80% scope.Polyreaction can be off and on, for example in the autoclave that stirs, or continuously, for example in tubular reactor, preferably in annular-pipe reactor, carries out.The particularly preferred Phillips PF method that is described among US-A 3 242 150 and the US-A 3 248 179 that is to use.Gas phase polymerization generally is to carry out under the pressure of 1-50 crust in 30-125 ℃ of scope.
Among above-mentioned polymerization process, particularly preferably be vapour phase polymerization, especially in gas-phase fluidized-bed reactor, solution polymerization and suspension polymerization are especially in annular-pipe reactor and stirred autoclave.Gas phase polymerization also can coagulate pattern with condensation or supercool to carry out, and wherein the part of recycle gas is cooled to below dew point and is recycled in the reactor as biphasic mixture.In addition, might use multi-region section reactor, wherein two polyreaction sections are connected to each other and polymkeric substance many times alternately passes this two sections.These two sections also can have different polymerizing conditions.This type of reactor for example is described among the WO 97/04015.If necessary, different or identical polymerization process also can be connected, thereby forms the polymerization cascade, for example with
The same in the technology.It also is possible using the parallel reactor of two or more identical or different processes to arrange.In addition, molecular weight regulator, for example hydrogen, or common additive such as static inhibitor also can be used for polyreaction.
Polyreaction preferably in single reactor, is especially carried out in Gas-phase reactor.When using catalyzer of the present invention, ethene obtains polyethylene of the present invention with the polyreaction with alpha-olefin of 3-12 carbon atom.Directly the polyethylene powders that obtains from reactor demonstrates very high homogeneity, and is therefore different with the situation of cascade process, carries out follow-up extruding not necessarily in order to obtain even product.
Meticulous mixing by each component, for example by the melt extrusion in forcing machine or kneader produce blend polymer process (referring to, for example " Polymer Blends ", Ullmann ' sEncyclopedia of Industrial Chemistry, the 6th edition, 1998, Electronic Release) usually with special difficulty.The high melt viscosity with low molecular weight component of bimodal polyethylene blend is extremely different.Although lower-molecular-weight component has suitable flowability being used to produce under about 190-210 ℃ the typical temperature of blend, high molecular weight component only is softened (" lentil soup ").Therefore the uniform mixing of two kinds of components is very difficult.In addition, well-known is that because thermal stresses and shearing force in forcing machine, high molecular weight component easily suffers damage, so the performance of blend is adversely affected.Therefore the mixing quality of this type of polyethylene blend usually is not satisfied.
Directly the mixing quality of the polyethylene powders that obtains from reactor can be tested by the section (" slicing machine section ") of analytic sample under opticmicroscope.Ununiformity is that the form with spot or " hickie " appears.Spot or " hickie " mainly be high molecular, full-bodied particle in low viscosity matrix (referring to, people such as U.Burkhardt for example, at " Aufbereiten vonPolymeren mit neuartigen Eigenschaften ", VDI-Verlag, D ü sseldorf 1995, p.71 in).This type of inclusion can reach the size of maximum 300 μ m, causes stress cracking and the brittle rupture that causes component.The mixing quality of polymkeric substance is good more, and viewed these inclusion just more less and more little.The mixing quality of polymkeric substance is measured quantitatively according to ISO 13949.According to this measuring method, slicing machine section is that the number of these inclusion and size are counted and come the mixing quality of polymkeric substance is determined grade according to a group analysis flow process from the specimen preparation of polymkeric substance.Do not have the polymer powder through extruding, the mixing quality the polyethylene that directly obtains from reactor preferably is lower than 3.
The preparation of polyethylene of the present invention in reactor can reduce energy expenditure, do not need follow-up blend process and makes the molecular weight distribution of various polymkeric substance and the simple control of molecular weight fraction become possibility.In addition, realized poly well blend.
The following example has illustrated the present invention but has not limited the scope of the invention.
Described observed value is measured with following manner:
The NMR sample is placed in the atmosphere of inert gases pipe and, if suitable, fusion.
1H-and
13Target solvents signals and their chemical shift are converted to the value with respect to TMS in being used as in the C-NMR spectrum.
Contents of ethylene is measured by IR according to ASTM D 6248-98.
Branch's number/1000 carbon atom is to utilize
13C-NMR, by James.C.Randall, JMS-REV.Macromol.Chem.Phys., C29 (2﹠amp; 3), the described method of 201-317 (1989) is measured, and with CH
3The total content (comprising end group) of group/1000 carbon atom is the basis.Should be greater than CH
3Side chain and ethyl especially, butyl and hexyl side chain branch number/1000 carbon atoms (eliminating end group) are similarly in this way measured.
The degree of branching in each polymer fractions can by with James.C.Randall, JMS-REV.Macromol.Chem.Phys., C29 (2﹠amp; 3), 201-317 (1989) is described
13The Holtrup method (W.Holtrup, Makromol.Chem.178,2335 (1977)) of C-NMR method associating is measured.
This density [g/cm
3] measure according to ISO 1183.
Molecular weight distribution and the average Mn that derives from from it, Mw, with the mensuration of Mw/Mn be by using method and placed in-line following chromatographic column based on DIN 55672, on WATERS150C, undertaken by the high-temperature gel permeation chromatography method, placed in-line chromatographic column: 3x SHODEX AT806MS, 1x SHODEX UT 807 and 1x SHODEX AT-G, operational condition: solvent: 1,2,4-trichlorobenzene (with 2 of 0.025wt%, 6-two-tertiary butyl-4-methylphenol is stable), flow velocity: 1ml/min, 500 μ l volume injected, temperature: 135 ℃, use the PE standard specimen to proofread and correct.Use WIN-GPC to estimate.
For the present invention, express general known being meant " high loading melt flow rate (MFR) " of phrase " HLMI " and according to ISO 1133 always under the temperature of the load of 21.6kg and 190 ℃, measure (190 ℃/21.6kg).
Mist degree be according to ASTM D 1003-00 on BYK Gardener Haze Guard PlusDevice, measure at the film 10 * 10cm of at least 5 1mm thickness.
Shock resistance is to measure down at-20 ℃ according to the falling weight impact test instrument of ISO 6603.
Stress cracking resistance (full notch creep test (FNCT)) be according to ISO DIS2 16770 under the pressure of 3.5Mbar and 80 ℃, measured in the 2 weight % solution that obtain soluble in water by Akropal N (N=10).
Spiral flow test is on Demag ET100-310, with the mold closing pressure of 100t and 3mm mouth mould with 250 ℃ material temperature, and the injection pressures of 1000 crust, the screw speed of 90mm/s, 30 ℃ die temperature and wall thickness 2mm measure.
Abbreviation in following table:
Cat. catalyzer
T (poly) polymerization temperature
M
wWeight-average molecular weight
M
nNumber-average molecular weight
Density polymers density
Vinyl/1000C refers to amount/per 1000 carbon atoms of vinyl
B/1000C refers to a branch/1000 carbon atoms, and it is CH
3Amount/comprise 1000 carbon atoms of end group
Brin 15%PE hmw refer to that the polyethylene with highest weight of 15 weight % has with greater than CH
3Branch's number/1000 carbon atom (eliminating end group) of side chain be the degree of branching of unit
Prod. obtain the throughput of the catalyzer of polymkeric substance/g catalyst system therefor/per hour by g
The Impact shock resistance is to measure down at-20 ℃ according to the falling weight impact test instrument of ISO 6603
The preparation of each component
Dichloro two (n-butyl cyclopentadienyl) closes hafnium and can be purchased from Crompton.
According to people such as Qian, Organometallics 2003,22, the method for 4312-4321, and preparation dichloro 2, two [1-(2, the 4-two chloro-6-aminomethyl phenyl imino-s) ethyl] pyridines of 6-close iron (II).Here; with 2 of 65.6g; 6-diacetyl pyridine (0.4mol); 2 of 170g; 4-two fluoro-6-monomethylanilines (0.483mol); the molecular sieve (4 dust) of silica gel 135 types of 32g and 160g stirred 5 hours down at 80 ℃ in the toluene of 1500ml, added silica gel 135 types of other 32g and the molecular sieve (4 dust) of 160g subsequently.Mixture stirred other 8 hours down at 80 ℃, and insoluble solid is filtered off, and used twice of toluene wash.Solvent distillates from the filtrate that in this way obtains, the methyl alcohol blending of residue and 200ml and subsequently 55 ℃ of stirrings 1 hour down.The suspension of Xing Chenging filters in this way, and the solid that is obtained methanol wash removes solvent then.Obtain 2 of 95g with 47% productive rate like this, two [1-(2, the 4-two chloro-6-aminomethyl phenyl imino-s) ethyl] pyridines of 6-.According to people such as Qian, Organometallics 2003,22, and the described method of 4312-4321 is carried out the reaction with iron(ic) chloride (II).
The preparation of hybrid catalyst system
Embodiment 1
A) carrier pre-treatment
XPO-2107, the spray-dired silica gel from Grace obtains baked under 600 ℃ 6 hours.
B) preparation of hybrid catalyst system
1.43g dichloro 2 (2.37mmol), 6-is two, and [1-(2,4-two chloro-6-aminomethyl phenyl imino-s) ethyl] pyridine closes iron (II), 9.98g dichloro two (n-butyl cyclopentadienyl) close the MAO (4.75M in toluene of hafnium and 443ml, 2.1mol) mixture at room temperature stirred 1 hour, what under agitation be added to 338g subsequently anticipates solid support material a) in 500ml toluene.Resulting solid is the catalyzer of 778.4g, and it still contains the solvent (based on gross weight and to support fully on carrier with whole components be that calculate on the basis) of 23.9wt%.
The polyreaction of catalyzer
Polyreaction is to carry out in the fluidized-bed reactor of the total pressure of diameter with 0.5m and 20 crust.Polymeric reaction temperature is 95 ℃, uses the catalyzer of embodiment 1, and it is added in the reactor with 38.97g/ hour speed.Ethene is with 40.7kg/ hour speed, and the 1-hexene is added in the reactor with 410g/ hour speed and the hydrogen speed with 2.1L/ hour.Same 4.62kg propane/hour, 0.33kg nitrogen/hour and 0.5g triisobutyl aluminium/hour be added in this reactor.Polymkeric substance is in the 30.1kg/h bottom discharge.The polymer properties that is obtained is summarised in the table 1.
The comparative example 1
According to preparing Z-type catalyst,, carry out polyreaction with the suspension method cascade by in first reactor, using ethene/hydrogen and in second reactor, using the ethene/1-butylene that contains 0.8 weight %1-butylene in method described in the EP-A-739937.Product data are shown in Table 1.
Table 1:
Be shaped as the small pieces of 1mm thickness on each comfortable Engel injection moulding machine of this polymkeric substance.This extrusion temperature is 225 ℃, and screw speed is that 116 commentaries on classics/min and injection speed are 50mm/s.Dwell time is 20s, and dwell pressure is 687 crust.
Table 2: poly performance
Claims (8)
1. polyethylene, it comprises the multipolymer of Alathon and/or ethene and 1-alkene and has the molecular weight distribution width Mw/Mn of 3-30,0.945-0.965g/cm
3Density, the weight-average molecular weight Mw of 50000g/mol-200000g/mol, the HLMI of 50-300g/10min also has 0.1-15 branch/1000 carbon atom, HLMI refers to high load melt index and measures under the temperature of the load of 21.6kg and 190 ℃ according to ISO1133, described polyethylene has at least 0.2 vinyl/1000 carbon atom, wherein the polyethylene of 1-15wt% with highest weight have more than 1 greater than CH
3The degree of branching of branch/1000 carbon atom of side chain.
2. according to the polyethylene of claim 1, it has bimodal at least short-chain branched distribution.
3. according to the polyethylene of claim 1 or 2, it has the degree of branching of 0.2-8 branch/1000 carbon atom.
4. according to the polyethylene of claim 1 or 2, it makes in single reactor.
5. comprise according to any one poly injection-molded item in the claim 1 to 4.
6. according to the injection-molded item of claim 5, it is lower than 94% according to the mist degree that ASTM D 1003-00 records.
7. according to any one injection-molded item among the claim 5-6, it is according to ISO DIS216770, and the anti-stress cracking FNCT that records in the 2 weight % aqueous solution at Akropal N under 3.5Mbar pressure and the 80 ℃ of conditions is 5h, wherein N=10 at least.
8. comprise according to any one poly thread cap in the claim 1 to 4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004020524A DE102004020524A1 (en) | 2004-04-26 | 2004-04-26 | Polyethylene for film, e.g. stretch film, used in carrier bags, contains ethylene homopolymers and/or copolymers of ethylene with 1-alkenes |
| DE102004020524.8 | 2004-04-26 | ||
| US58753304P | 2004-07-13 | 2004-07-13 | |
| US60/587,533 | 2004-07-13 | ||
| PCT/EP2005/004412 WO2005103096A1 (en) | 2004-04-26 | 2005-04-25 | Polyethylene for injection moldings |
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| CN1976957B true CN1976957B (en) | 2011-01-26 |
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| CN2005800213492A Active CN101098899B (en) | 2004-04-26 | 2005-04-25 | Polyethylene and catalyst composition for its preparation |
| CN2010102604652A Pending CN101935369A (en) | 2004-04-26 | 2005-04-25 | Polyethylene and be used to prepare its catalyst composition |
| CN2005800213685A Active CN1976958B (en) | 2004-04-26 | 2005-04-25 | Polyethylene and catalyst composition for its preparation |
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| CN2005800213685A Active CN1976958B (en) | 2004-04-26 | 2005-04-25 | Polyethylene and catalyst composition for its preparation |
| CN2010101716114A Expired - Fee Related CN101824111B (en) | 2004-04-26 | 2005-04-25 | Polyethylene and catalyst composition for its preparation |
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